Pesticides containing a bicyclic bisamide structure

ABSTRACT

Compounds of formula (I), wherein the substituents are as defined in claim  1 , and the agrochemically acceptable salts and all stereoisomers and tautomeric forms of the compounds of formula I can be used as agrochemical active ingredients and can be prepared in a manner known per se.

This application is a 371 of International Application No.PCT/EP2007/001283 filed Feb. 14, 2007, the contents of which areincorporated herein by reference, and which claims priority to EP06003094.7 filed Feb. 16, 2006.

The present invention relates to bicyclic bisamide derivatives, toprocesses for their preparation, to compositions comprising thosecompounds, and to their use for controlling insects or representativesof the order Acarina.

Bisamide derivatives with insecticidal action are known and described,for example, in US 2003/0229050 and WO 2005/085234.

There have now been found novel bicyclic bisamide derivatives withpesticidal properties. The present invention accordingly relates tocompounds of formula I

wherein

G₁, G₂, G₃ and G₄ form together with the two carbon atoms to which G₁and G₄ are attached, an aromatic ring system; wherein

G₁ is nitrogen, sulfur, oxygen, a direct bond or C—R_(5a);

G₂ is nitrogen, sulfur, oxygen, a direct bond or C—R_(5b);

G₃ is nitrogen, sulfur, oxygen, a direct bond or C—R_(5c);

G₄ is nitrogen, sulfur, oxygen, a direct bond or C—R_(5d); with theprovisos that

a) at least one substituent G represents nitrogen, sulfur or oxygen,

b) not more than 1 substituent G can at the same time form a directbond,

c) not more than 2 substituents G can be oxygen or sulfur, and

d) 2 substituents G as oxygen and/or sulfur are separated by at leastone carbon atom; each of R_(1a), R_(1b), R_(5a), R_(5b), R_(5c), andR_(5d) which may be the same or different, represents hydrogen, halogen,nitro, cyano, hydroxy, CHO, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl,C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl,C₃-C₆halocycloalkyl, C₁-C₄alkoxy, C₁-C₄alkoxy-C₁-C₄alkoxy-C₁-C₄alkyl,C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio,C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄alkylsulfonyl-C₁-C₄alkyl,C_(r)C₄alkylsulfoximino-C₁-C₄alkyl, C₁-C₄alkylamino, C₂-C₄dialkylamino,C₃-C₆cycloalkylamino, C₁-C₆alkyl-C₃-C₆cycloalkylamino,C₂-C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl,C₃-C₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy,C₂-C₆alkylaminocarbonyloxy, C₃-C₆dialkylaminocarbonyloxy,C₁-C₄alkoxyimino-C₁-C₄alkyl, C₃-C₆trialkylsilyl, phenyl, benzyl orphenoxy; or phenyl, benzyl or phenoxy mono-, di- or trisubstituted byhalogen, cyano, nitro, halogen, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl,C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl,C₃-C₆halocycloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio,C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄alkylamino, C₂-C₄dialkylamino, C₃-C₆cycloalkylamino,C₁-C₆alkyl-C₃-C₈cycloalkylamino, C₂-C₄alkylcarbonyl,C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₆dialkylaminocarbonyl,C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy,C₃-C₆dialkylaminocarbonyloxy or C₃-C₆trialkylsilyl;

each of R₂ and R₃, which may be the same or different, representshydrogen, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl or C₃-C₈cycloalkyl; orC₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl or C₃-C₈cycloalkyl substituted byone or more substituents selected from halogen nitro, cyano, hydroxy,C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio,C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino,C₂-C₄dialkylamino, C₃-C₆cycloalkylamino andC₁-C₆alkyl-C₃-C₆cycloalkylamino;

D is 2-pyridyl, 3-pyridyl or 4-pyridyl; or phenyl, 2-pyridyl, 3-pyridylor 4-pyridyl mono-, di- or trisubstituted by C₁-C₆alkyl,C₃-C₆cycloalkyl, C₁-C₆haloalkyl, halogen, cyano, C₁-C₄alkoxy,C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄haloalkylsulfinyl or C₁-C₄haloalkylsulfonyl; orD is a group

or D is additionally phenyl if Z₁ is sulfur;

R₄, R₄′, R₁₀, R₁₇, and R₁₉ independently from each other, are hydrogen,C₁-C₆alkyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, halogen, cyano,C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₂-C₄alkoxycarbonyl, C₁-C₄alkylthio,C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄haloalkylsulfinyl or C₁-C₄haloalkylsulfonyl;

R₅, R₆, R₈, R₁₁, R₁₂, R₁₅, R₁₆ and R₁₈ independently from each other,are C₁-C₆alkyl, or C₁-C₆alkyl mono-, di- or trisubstituted by halogen,cyano, nitro, hydroxy, C₁-C₄alkoxy, C₂-C₄alkoxycarbonyl, C₁-C₄alkylthio,C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino,C₂-C₄dialkylamino or C₃-C₆cycloalkylamino; or are phenyl, 2-pyridyl,3-pyridyl, 4-pyridyl; or are phenyl, 2-pyridyl, 3-pyridyl or 4-pyridylmono-, di- or trisubstituted by C₁-C₆alkyl, C₃-C₆cycloalkyl,C₁-C₆haloalkyl, halogen, cyano, C₁-C₄alkoxy, C₁-C₄haloalkoxy,C₁-C₄alkylthio, C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄haloalkylsulfinyl or C₁-C₄haloalkylsulfonyl;

R₇, R₉, R₁₃ and R₁₄ independently from each other, are hydrogen,C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₃-C₆alkenylor C₃-C₆haloalkenyl;

R₂₀ is hydrogen, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, orC₃-C₆cycloalkyl; or is C₁-C₆alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl or C₃-C₆cycloalkyl substituted with one, two or three substituents selected fromthe group consisting of halogen, cyano, nitro, hydroxy, C₁-C₄alkyl,C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄alkylsulfoximino, C₂-C₆ alkoxycarbonyl, C₂-C₆alkylcarbonyl, C₂-C₆trialkylsilyl, benzyl, phenoxy and a three- toten-membered, monocyclic or fused bicyclic ring system which may bearomatic, partially saturated or fully saturated, wherein thesix-membered aromatic ring system contains at least one heteroatomselected from the group consisting of oxygen, nitro and sulfur; it beingpossible for said benzyl, phenoxy and three- to ten-membered, monocyclicor fused bicyclic ring system in turn to be substituted by one to threesubstituents independently selected from the group consisting ofC₁-C₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, C₁-C₄haloalkyl,C₂-C₄haloalkenyl, C₂-C₄haloalkynyl, C₂-C₆halocycloalkyl, halogen, cyano,nitro, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄alkylsulfoximino, C₁-C₄alkylamino,C₂-C₆dialkylamino, C₃-C₆cycloalkylamino,C₁-C₄alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl,C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₂-C₈ dialkylaminocarbonyland C₂-C₆ trialkylsilyl;

it being possible for said three- to ten-membered, monocyclic or fusedbicyclic ring system to be spiro-bonded to the C₃-C₆cycloalkyl group;

or R₂₀ is C₁-C₄alkoxy, C₁-C₄alkylamino, C₂-C₈dialkylamino, C₂-C₆cycloalkylamino, C₂-C₆alkoxycarbonyl or C₂-C₆alkylcarbonyl;

or R₂₀ is 3-oxetanyl, 3-thietanyl, 1-oxo-3-thietanyl,1,1-dioxo-3-thietanyl, 1-imino-1-oxo-3-thietanyl, 3-azetdinyl, eachoptionally substituted with one to five substituents independentlyselected from C₁-C₄ alkyl, C₁-C₄ haloalkyl, halogen, cyano; each of Z₁and Z₂, which may be the same or different, represents oxygen or sulfur;

and agronomically acceptablesalts/isomers/enantiomers/tautomers/N-oxides of those compounds.

Compounds I which have at least one basic centre can form, for example,acid addition salts, for example with strong inorganic acids such asmineral acids, for example perchloric acid, sulfuric acid, nitric acid,nitrose acid, a phosphorus acid or a hydrohalic acid, with strongorganic carboxylic acids, such as C₁-C₄alkanecarboxylic acids which areunsubstituted or substituted, for example by halogen, for example aceticacid, such as saturated or unsaturated dicarboxylic acids, for exampleoxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid orphthalic acid, such as hydroxycarboxylic acids, for example ascorbicacid, lactic acid, malic acid, tartaric acid or citric acid, or such asbenzoic acid, or with organic sulfonic acids, such as C₁-C₄alkane- orarylsulfonic acids which are unsubstituted or substituted, for exampleby halogen, for example methane- or p-toluenesulfonic acid. Compounds Iwhich have at least one acidic group can form, for example, salts withbases, for example mineral salts such as alkali metal or alkaline earthmetal salts, for example sodium, potassium or magnesium salts, or saltswith ammonia or an organic amine, such as morpholine, piperidine,pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-,diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- ortrihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.Where appropriate, the corresponding internal salts can furthermore beformed. Preferred within the scope of the invention are agrochemicallyadvantageous salts; however, the invention also encompasses salts whichhave disadvantage for agrochemical use, for example salts which aretoxic to bees or fish, and which are employed, for example, for theisolation or purification of free compounds I or agrochemicallyutilizable salts thereof. Owing to the close relationship between thecompounds I in free form and in the form of their salts, for thepurposes of the invention the free compounds I or their saltshereinabove and hereinbelow are respectively to be understood asincluding, where appropriate, the corresponding salts or the freecompounds I. The same applies analogously to tautomers of compounds Iand salts thereof. In general, the free form is preferred in each case.

The alkyl groups occurring in the definitions of the substituents can bestraight-chain or branched and are, for example, methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyland hexyl and their branched isomers. Alkoxy, alkenyl and alkynylradicals are derived from the alkyl radicals mentioned. The alkenyl andalkynyl groups can be mono- or polyunsaturated.

Halogen is generally fluorine, chlorine, bromine or iodine. This alsoapplies, correspondingly, to halogen in combination with other meanings,such as haloalkyl or halophenyl.

Haloalkyl groups preferably have a chain length of from 1 to 6 carbonatoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl,trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl,1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl,difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

Suitable haloalkenyl groups are alkenyl groups which are mono- orpolysubstituted by halogen, halogen being fluorine, chlorine, bromineand iodine and in particular fluorine and chlorine, for example2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl,3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and4,4,4-trifluorobut-2-en-1-yl. Among the C₃-C₂₀alkenyl groups which aremono-, di- or trisubstituted by halogen, preference is given to thosehaving a chain length of from 3 to 5 carbon atoms.

Suitable haloalkynyl groups are, for example, alkynyl groups which aremono- or polysubstituted by halogen, halogen being bromine, iodine andin particular fluorine and chlorine, for example 3-fluoropropynyl,3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and4,4,4-trifluorobut-2-yn-1-yl. Among the alkynyl groups which are mono-or polysubstituted by halogen, preference is given to those having achain length of from 3 to 5 carbon atoms.

Alkoxy groups preferably have a preferred chain length of from 1 to 6carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy,i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and also theisomeric pentyloxy and hexyloxy radicals; preferably methoxy and ethoxy.

Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl,propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl,isobutoxycarbonyl, sec-butoxycarbonyl or tertbutoxycarbonyl; preferablymethoxycarbonyl or ethoxycarbonyl. Haloalkoxy groups preferably have achain length of from 1 to 6 carbon atoms. Haloalkoxy is, for example,fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy,1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy,2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferablydifluoromethoxy, 2-chloroethoxy and trifluoromethoxy. Alkylthio groupspreferably have a chain length of from 1 to 6 carbon atoms. Alkylthiois, for example, methylthio, ethylthio, propylthio, isopropylthio,n-butylthio, isobutylthio, sec-butylthio or tertbutylthio, preferablymethylthio and ethylthio. Alkylsulfinyl is, for example, methylsulfinyl,ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl,isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl; preferablymethylsulfinyl and ethylsulfinyl.

Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl,propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl,sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl orethylsulfonyl.

Alkylamino is, for example, methylamino, ethylamino, n-propylamino,isopropylamino or the isomeric butylamines. Dialkylamino is, forexample, dimethylamino, methylethylamino, diethylamino,n-propylmethylamino, dibutylamino and diisopropylamino. Preference isgiven to alkylamino groups having a chain length of from 1 to 4 carbonatoms.

Alkoxyalkyl groups preferably have a chain length of 1 to 6 carbonatoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl,ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl,isopropoxymethyl or isopropoxyethyl.

Alkylthioalkyl groups preferably have from 1 to 8 carbon atoms.Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl,ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl,isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethylor butylthiobutyl.

The cycloalkyl groups preferably have from 3 to 6 ring carbon atoms, forexample cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Phenyl,also as part of a substituent such as phenoxy, benzyl, benzyloxy,benzoyl, phenylthio, phenylalkyl, phenoxyalkyl, may be substituted. Inthis case, the substituents can be in ortho, meta and/or para position.The preferred substituent positions are the ortho and para positions tothe ring attachment point.

According to the present invention, a three- to ten-membered monocyclicor fused bicyclic ring system which may be aromatic, partially saturatedor fully saturated is, depending of the number of ring members, forexample, selected from the group consisting of

cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, where saidcycloalkylgroups for their part may be preferably unsubstituted orsubstituted by C₁-C₆alkyl or halogen, or is naphthyl or the followingheterocyclic groups: pyrrolyl; pyridyl; pyrazolyl; pyrimidyl; pyrazinyl;imidazolyl; thiadiazolyl; quinazolinyl; furyl; oxadiazolyl; indolizinyl;pyranyl; isobenzofuranyl; thienyl; naphthyridinyl;(1-methyl-1H-pyrazol-3-yl)-; (1-ethyl-1H-pyrazol-3-yl)-;(1-propyl-1H-pyrazol-3-yl)-; (1H-pyrazol-3-yl)-;(1,5-dimethyl-1H-pyrazol-3-yl)-; (4-chloro-1-methyl-1H-pyrazol-3-yl)-;(1H-pyrazol-1-yl)-; (3-methyl-1H-pyrazol-1-yl)-;(3,5-dimethyl-1H-pyrazol-1-yl)-; (3-isoxazolyl)-;(5-methyl-3-isoxazolyl)-; (3-methyl-5-isoxazolyl)-; (5-isoxazolyl)-;(1H-pyrrol-2-yl)-; (1-methyl-1H-pyrrol-2-yl)-; (1H-pyrrol-1-yl)-;(1-methyl-1H-pyrrol-3-yl)-; (2-furanyl)-; (5-methyl-2-furanyl)-;(3-furanyl)-; (5-methyl-2-thienyl)-; (2-thienyl)-; (3-thienyl)-;(1-methyl-1H-imidazol-2-yl)-; (1H-imidazol-2-yl)-;(1-methyl-1H-imidazol-4-yl)-; (1-methyl-1H-imidazol-5-yl)-;(4-methyl-2-oxazolyl)-; (5-methyl-2-oxazolyl)-; (2-oxazolyl)-;(2-methyl-5-oxazolyl)-; (2-methyl-4-oxazolyl)-; (4-methyl-2-thiazolyl)-;(5-methyl-2-thiazolyl)-; (2-thiazolyl)-; (2-methyl-5-thiazolyl)-;(2-methyl-4-thiazolyl)-; (3-methyl-4-isothiazolyl)-;(3-methyl-5-isothiazolyl)-; (5-methyl-3-isothiazolyl)-;(1-methyl-1H-1,2,3-triazol-4-yl)-; (2-methyl-2H-1,2,3-triazol-4-yl)-;(4-methyl-2H-1,2,3-triazol-2-yl)-; (1-methyl-1H-1,2,4-triazol-3-yl)-;(1,5-dimethyl-1H-1,2,4-triazol-3-yl)-;(3-methyl-1H-1,2,4-triazol-1-yl)-; (5-methyl-1H-1,2,4-triazol-1-yl)-;(4,5-dimethyl-4H-1,2,4-triazol-3-yl)-;(4-methyl-4H-1,2,4-triazol-3-yl)-; (4H-1,2,4-triazol-4-yl)-;(5-methyl-1,2,3-oxadiazol-4-yl)-; (1,2,3-oxadiazol-4-yl)-;(3-methyl-1,2,4-oxadiazol-5-yl)-; (5-methyl-1,2,4-oxadiazol-3-yl)-;(4-methyl-3-furazanyl)-; (3-furazanyl)-;(5-methyl-1,2,4-oxadiazol-2-yl)-; (5-methyl-1,2,3-thiadiazol-4-yl)-;(1,2,3-thiadiazol-4-yl)-; (3-methyl-1,2,4-thiadiazol-5-yl)-;(5-methyl-1,2,4-thiadiazol-3-yl)-; (4-methyl-1,2,5-thiadiazol-3-yl)-;(5-methyl-1,3,4-thiadiazol-2-yl)-; (1-methyl-1H-tetrazol-5-yl)-;(1H-tetrazol-5-yl)-; (5-methyl-1H-tetrazol-1-yl)-;(2-methyl-2H-tetrazol-5-yl)-; (2-ethyl-2H-tetrazol-5-yl)-;(5-methyl-2H-tetrazol-2-yl)-; (2H-tetrazol-2-yl)-; (2-pyridyl)-;(6-methyl-2-pyridyl)-; (4-pyridyl)-; (3-pyridyl)-;(6-methyl-3-pyridazinyl)-; (5-methyl-3-pyridazinyl)-; (3-pyridazinyl)-;(4,6-dimethyl-2-pyrimidinyl)-; (4-methyl-2-pyrimidinyl)-;(2-pyrimidinyl)-; (2-methyl-4-pyrimidinyl)-; (2-chloro-4-pyrimidinyl)-;(2,6-dimethyl-4-pyrimidinyl)-; (4-pyrimidinyl)-;(2-methyl-5-pyrimidinyl)-; (6-methyl-2-pyrazinyl)-; (2-pyrazinyl)-;(4,6-dimethyl-1,3,5-triazin-2-yl)-; (4,6-dichloro-1,3,5-triazin-2-yl)-;(1,3,5-triazin-2-yl)-; (4-methyl-1,3,5-triazin-2-yl)-;(3-methyl-1,2,4-triazin-5-yl)-; (3-methyl-1,2,4-triazin-6-yl)-;

wherein each R₂₆ is methyl, each R₂₇ and each R₂₆ are independentlyhydrogen, C₁-C₃alkyl, C₁-C₃alkoxy, C₁-C₃alkylthio or trifluoromethyl, X₄is oxygen or sulfur and r is 1, 2, 3 or 4.

Examples for a three- to ten-membered, monocyclic or fused bicyclic ringsystem which is spiro-bonded to the C₃-C₆cycloalkyl group of thesubstituent R₂₀ are

Where no free valency is indicated in those definitions, for example asin

the linkage site is located at the carbon atom labelled “CH” or in acase such as, for example,

at the bonding site indicated at the bottom left.

Preferably Z₁ and/or Z₂ is oxygen.

Preferably R₄ is hydrogen.

Further compounds of formula I are preferred, wherein R₂ and/or R₃ ishydrogen.

R₂₀ is preferably hydrogen, methyl, ethyl, i-propyl, tert.-butyl,CH₂—C₃H₅, C(CH₂CH₂)—C₃H₅, C(CH₃)₂CH₂SCH₃, C(CH₃)₂CH₂S(O)CH₃,C(CH₃)₂CH₂S(O)₂CH₃, CH₂CN, CH(CH₃)CH₃SCH₃, CH(CH₃)CH₃S(O)CH₃ orCH(CH₃)CH₃S(O)₂CH₃, 3-methyl-thietan-3-yl, 1-oxo-3-methyl-thietan-3-ylor 1,1-dioxo-3-methyl-thietan-3-yl, in particular hydrogen, methyl,ethyl, i-propyl, tert.-butyl, CH₂—C₃H₅, C(CH₂CH₂)—C₃H₅, C(CH₃)₂CH₂SCH₃,C(CH₃)₂CH₂S(O)CH₃, C(CH₃)₂CH₂S(O)₂CH₃, CH₂CN, CH(CH₃)CH₃SCH₃,CH(CH₃)CH₃S(O)CH₃ or CH(CH₃)CH₃S(O)₂CH₃.

Special emphasis should also be given to compounds of formula I whereinD is a group D₁, wherein R₅ is 2-pyridyl which can be substituted byhalogen, preferably which is monosubstituted by chloro at the 3-positionof the pyridine ring and R₄ is halogen preferably chloro or bromo,C₁-C₆haloalkyl, C₁-C₄haloalkoxy most preferably OCF₂H or2,2,2-trifluoroethoxy, preferably C₁-C₆haloalkyl, most preferablytrifluoromethyl.

Special mention should be made of compounds of formula I wherein

each of R_(1a), R_(1b), R_(5a), R_(5b), R_(5c), and R_(5d) which may bethe same or different, represents hydrogen, halogen, cyano, hydroxy,CHO, C₁-C₆alkyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₁-C₄alkoxy,C₁-C₄alkoxy-C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄alkylsulfonyl-C₁-C₄alkyl,C₁-C₄alkylsulfoximino-C₁-C₄alkyl, C₂-C₄dialkylamino orC₁-C₄alkoxyimino-C₁-C₄alkyl.

An outstanding group of compounds of formula I is represented by theformula Ib

wherein G₁, G₂, G₃ and G₄ have the meaning as given for formula I above;

R₁₀₁ is halogen, haloalkyl, haloalkoxy, alkoxy, especiallydifluoromethyl, trifluoromethyl, chlorine, bromine, OCF₂H₂O—CH₂—CF₃ orOCH₃, in particular halogen, haloalkyl, haloalkoxy, especiallytrifluoromethyl, chlorine, bromine, OCF₂H or O—CH₂—CF₃;

R₁₀₂ is halogen, C₁-C₆-alkyl, C₂-C₆-alkynyl, cyano, especially methyl,ethynyl, chlorine or bromine; in particular halogen, C₁-C₆-alkyl,especially methyl, chlorine or bromine; and

R₁₀₃ is methyl, ethyl, i-propyl, tert.-butyl, CH₂—C₃H₅, C(CH₂CH₂)—C₃H₆,C(CH₃)₂CH₂SCH₃, C(CH₃)₂CH₂S(O)CH₃ or C(CH₃)₂CH₂S(O)₂CH₃, CH₂CN,CH(CH₃)CH₃SCH₃, CH(CH₃)CH₃S(O)CH₃ or CH(CH₃)CH₃S(O)₂CH₃,3-methyl-thietan-3-yl, 1-oxo-3-methyl-thietan-3-yl or1,1-dioxo-3-methyl-thietan-3-yl; in particular methyl, ethyl, i-propyl,tert.-butyl, CH₂—C₃H₅, C(CH₂CH₂)—C₃H₅, C(CH₃)₂CH₂SCH₃, C(CH₃)₂CH₂S(O)CH₃or C(CH₃)₂CH₂S(O)₂CH₃, CH₂CN, CH(CH₃)CH₃SCH₃, CH(CH₃)CH₃S(O)CH₃ orCH(CH₃)CH₃S(O)₂CH₃.

Especially preferred compounds of formula I are represented by thefollowing formulae:

in particular formula (Ic);

wherein

R_(1a) is preferably hydrogen, C₁-C₄alkyl, C₂-C₄alkynyl, halogen orcyano;

R₂₀ is preferably hydrogen, C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl,C₁-C₆alkylsulfonyl-C₁-C₆alkyl, C₁-C₆alkylsulfinyl-C₁-C₆alkyl,thiethan-3-yl, thiethan-3-yl substituted by C₁-C₄alkyl, preferably3-methyl-thietan-3-yl,

in particular hydrogen, C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl,C₁-C₆alkylsulfonyl-C₁-C₆alkyl, C₁-C₆alkylsulfinyl-C₁-C₆alkyl,

R₁₀₀ is preferably halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy orC₁-C₆haloalkoxy; in particular halogen, C₁-C₆alkyl, C₁-C₆haloalkyl orC₁-C₆haloalkoxy;

R_(1c) is hydrogen, CH₃, CH₂CH₃, OCH₃, SCH₃, Cl, O, NH₂, Br, NHCH₃ orN(CH₃)₂;

R_(1d) is hydrogen or CH₃; in particular CH₃; and

R_(1e) is hydrogen, halogen or CH₃; preferably hydrogen.

Further preferred embodiments of the present invention are theembodiments E1 to E99, which are defined as compounds of formula I whichare represented by one formula selected from the group consisting of theformulae T1 to T99 as described below,

wherein in formulae T1 to T99

R_(1a) is preferably hydrogen, C₁-C₄alkyl, C₂-C₄alkynyl, halogen orcyano; in particular chloro or methyl;

R₂₀ is preferably hydrogen, C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl,C₁-C₆alkylsulfonyl-C₁-C₆alkyl, C₁-C₆alkylsulfinyl-C₁-C₆alkyl,thiethan-3-yl, thiethan-3-yl substituted by C₁-C₄alkyl, preferably3-methyl-thietan-3-yl,

in particular hydrogen, C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl,C₁-C₆alkylsulfonyl-C₁-C₆alkyl, C₁-C₆alkylsulfinyl-C₁-C₆alkyl,

especially isopropyl; and

R₁₀₀ is preferably halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy orC₁-C₆haloalkoxy; in particular halogen, C₁-C₆alkyl, C₁-C₆haloalkyl orC₁-C₆alkoxy; in particular trifluoromethyl, difluoromethyl, methoxy,bromo, chloro or 2,2,2-trifluoroethoxy.

For example, embodiment E1 is represented by the compounds of formula T1

wherein

R_(1a) is preferably hydrogen, C₁-C₄alkyl, C₂-C₄alkynyl, halogen orcyano; in particular chloro or methyl;

R₂₀ is preferably hydrogen, C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl,C₁-C₆alkylsulfonyl-C₁-C₆alkyl, C₁-C₆alkylsulfinyl-C₁-C₆alkyl,thiethan-3-yl, thiethan-3-yl substituted by C₁-C₄alkyl, preferably3-methyl-thietan-3-yl,

in particular hydrogen, C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl,C₁-C₆alkylsulfonyl-C₁-C₆alkyl, C₁-C₆alkylsulfinyl-C₁-C₆alkyl,

especially isopropyl; and

R₁₀₀ is preferably halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy orC₁-C₆haloalkoxy; in particular halogen, C₁-C₆alkyl, C₁-C₆haloalkyl orC₁-C₆alkoxy; in particular trifluoromethyl, difluoromethyl, methoxy,bromo, chloro or 2,2,2-trifluoroethoxy.

Embodiments E2 to E99 are defined accordingly.

The process according to the invention for preparing compounds of theformula I is carried out analogously to known processes, for example asdescribed in described, for example, in US 2003/0229050 and WO2005/085234.

The general preparation of the compounds of formula I is illustrated inthe following reaction schemes:

TABLE B Intermediates: Anthranilic Acids And Methyl Ester DerivativesMS/NMR

¹H-NMR (MeOD₄, 400 MHz): 7.51 (m, 1 H), 7.05 (d, 1 H), 6.55 (d, 1 H),6.33 (m, 1 H) ppm

178/179 (M + H)⁺

212/214 (M + H)⁺

256/258 (M + H)⁺

318/319 (M + H)⁺

192/193 (M + H)⁺

203/204 (M + H)⁺

288/289 (M + H)⁺

202/203 (M + H)⁺

189/190 (M + H)⁺

280/282 (M + H)⁺

203/204 (M + H)⁺

290/292 (M + H)⁺

226/228 (M + H)⁺

189/190 (M + H)⁺

228/230 (M − H)⁻

¹H-NMR (CDCl₃, 400 MHz): 8.36 (s, 1 H), 7.60 (s, 1 H), 4.02 (s, 3 H),3.99 (s, 3 H) ppm

274/276 (M + Na)⁺

226/228 (M + H)⁺

The starting compounds and intermediates of the reaction schemes areknown or can be prepared according to methods known to a person skilledin the art.

The reactants can be reacted in the presence of a base. Examples ofsuitable bases are alkali metal or alkaline earth metal hydroxides,alkali metal or alkaline earth metal hydrides, alkali metal or alkalineearth metal amides, alkali metal or alkaline earth metal alkoxides,alkali metal or alkaline earth metal acetates, alkali metal or alkalineearth metal carbonates, alkali metal or alkaline earth metaldialkylamides or alkali metal or alkaline earth metal alkylsilylamides,alkylamines, alkylenediamines, free or N-alkylated saturated orunsaturated cycloalkylamines, basic heterocycles, ammonium hydroxidesand carbocyclic amines. Examples which may be mentioned are sodiumhydroxide, sodium hydride, sodium amide, sodium methoxide, sodiumacetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide,potassium carbonate, potassium hydride, lithium diisopropylamide,potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine,diisopropylethylamine, triethylenediamine, cyclohexylamine,N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine,4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine,benzyltrimethylammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU).

The reactants can be reacted with each other as such, i.e. withoutadding a solvent or diluent. In most cases, however, it is advantageousto add an inert solvent or diluent or a mixture of these. If thereaction is carried out in the presence of a base, bases which areemployed in excess, such as triethylamine, pyridine, N-methylmorpholineor N,N-diethylaniline, may also act as solvents or diluents.

The reaction is advantageously carried out in a temperature range fromapproximately −80° C. to approximately +140° C., preferably fromapproximately −30° C. to approximately +100° C., in many cases in therange between ambient temperature and approximately +80° C.

A compound I can be converted in a manner known per se into anothercompound I by replacing one or more substituents of the startingcompound I in the customary manner by (an)other substituent(s) accordingto the invention.

Depending on the choice of the reaction conditions and startingmaterials which are suitable in each case, it is possible, for example,in one reaction step only to replace one substituent by anothersubstituent according to the invention, or a plurality of substituentscan be replaced by other substituents according to the invention in thesame reaction step.

Salts of compounds I can be prepared in a manner known per se. Thus, forexample, acid addition salts of compounds I are obtained by treatmentwith a suitable acid or a suitable ion exchanger reagent and salts withbases are obtained by treatment with a suitable base or with a suitableion exchanger reagent.

Salts of compounds I can be converted in the customary manner into thefree compounds I, acid addition salts, for example, by treatment with asuitable basic compound or with a suitable ion exchanger reagent andsalts with bases, for example, by treatment with a suitable acid or witha suitable ion exchanger reagent.

Salts of compounds I can be converted in a manner known per se intoother salts of compounds I, acid addition salts, for example, into otheracid addition salts, for example by treatment of a salt of inorganicacid such as hydrochloride with a suitable metal salt such as a sodium,barium or silver salt, of an acid, for example with silver acetate, in asuitable solvent in which an inorganic salt which forms, for examplesilver chloride, is insoluble and thus precipitates from the reactionmixture.

Depending on the procedure or the reaction conditions, the compounds I,which have salt-forming properties can be obtained in free form or inthe form of salts.

The compounds I and, where appropriate, the tautomers thereof, in eachcase in free form or in salt form, can be present in the form of one ofthe isomers which are possible or as a mixture of these, for example inthe form of pure isomers, such as antipodes and/or diastereomers, or asisomer mixtures, such as enantiomer mixtures, for example racemates,diastereomer mixtures or racemate mixtures, depending on the number,absolute and relative configuration of asymmetric carbon atoms whichoccur in the molecule and/or depending on the configuration ofnon-aromatic double bonds which occur in the molecule; the inventionrelates to the pure isomers and also to all isomer mixtures which arepossible and is to be understood in each case in this sense hereinaboveand hereinbelow, even when stereochemical details are not mentionedspecifically in each case.

Diastereomer mixtures or racemate mixtures of compounds I, in free formor in salt form, which can be obtained depending on which startingmaterials and procedures have been chosen can be separated in a knownmanner into the pure diasteromers or racemates on the basis of thephysicochemical differences of the components, for example by fractionalcrystallization, distillation and/or chromatography.

Enantiomer mixtures, such as racemates, which can be obtained in asimilar manner can be resolved into the optical antipodes by knownmethods, for example by recrystallization from an optically activesolvent, by chromatography on chiral adsorbents, for examplehigh-performance liquid chromatography (HPLC) on acetyl celulose, withthe aid of suitable microorganisms, by cleavage with specific,immobilized enzymes, via the formation of inclusion compounds, forexample using chiral crown ethers, where only one enantiomer iscomplexed, or by conversion into diastereomeric salts, for example byreacting a basic end-product racemate with an optically active acid,such as a carboxylic acid, for example camphor, tartaric or malic acid,or sulfonic acid, for example camphorsulfonic acid, and separating thediastereomer mixture which can be obtained in this manner, for exampleby fractional crystallization based on their differing solubilities, togive the diastereomers, from which the desired enantiomer can be setfree by the action of suitable agents, for example basic agents.

Pure diastereomers or enantiomers can be obtained according to theinvention not only by separating suitable isomer mixtures, but also bygenerally known methods of diastereoselective or enantioselectivesynthesis, for example by carrying out the process according to theinvention with starting materials of a suitable stereochemistry.

It is advantageous to isolate or synthesize in each case thebiologically more effective isomer, for example enantiomer ordiastereomer, or isomer mixture, for example enantiomer mixture ordiastereomer mixture, if the individual components have a differentbiological activity.

The compounds I and, where appropriate, the tautomers thereof, in eachcase in free form or in salt form, can, if appropriate, also be obtainedin the form of hydrates and/or include other solvents, for example thosewhich may have been used for the crystallization of compounds which arepresent in solid form.

The compounds I according to the invention are preventively and/orcuratively valuable active ingredients in the field of pest control,even at low rates of application, which have a very favorable biocidalspectrum and are well tolerated by warm-blooded species, fish andplants. The active ingredients according to the invention act againstall or individual developmental stages of normally sensitive, but alsoresistant, animal pests, such as insects or representatives of the orderAcarina. The insecticidal or acaricidal activity of the activeingredients according to the invention can manifest itself directly,i.e. in destruction of the pests, which takes place either immediatelyor only after some time has elapsed, for example during ecdysis, orindirectly, for example in a reduced oviposition and/or hatching rate, agood activity corresponding to a destruction rate (mortality) of atleast 50 to 60%.

Examples of the abovementioned animal pests are:

from the order Acarina, for example,

Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp.,Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa,Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae,Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp.,Olygonychus pratensis, Ornithodoros spp., Panonychus spp.,Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp.,Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp.and Tetranychus spp.;

from the order Anoplura, for example,

Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. andPhylloxera spp.;

from the order Coleoptera, for example,

Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis,Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp.,Epilachna spp., Eremnus spp., Leptinotarsa decemLineata, Lissorhoptrusspp., Melolontha spp., Orycaephilus spp., Otiorhynchus spp., Phlyctinusspp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae,Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. andTrogoderma spp.;

from the order Diptera, for example,

Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphoraerythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebraspp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilusspp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp.,Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseoliaspp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletispomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. andTipula spp.;

from the order Heteroptera, for example,

Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp.,Eurygaster spp., Leptocorisa spp., Nezara spp., Piesma spp., Rhodniusspp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp.;

from the order Homoptera, for example,

Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp.,Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplasterspp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccushesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp.,Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp.,Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp.,Parlatoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp.,Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotusspp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphisspp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae andUnaspis citri;

from the order Hymenoptera, for example,

Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpiniapolytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprionspp., Solenopsis spp. and Vespa spp.;

from the order Isoptera, for example,

Reticulitermes spp.;

from the order Lepidoptera, for example,

Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabamaargillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp.,Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella,Carposina nipponensis, Chilo spp., Choristoneura spp., Clysiaambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp.,Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydiaspp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp.,Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp.,Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis,Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella,Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp.,Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp.,Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea,Pectinophora gossypiela, Phthorimaea operculella, Pieris rapae, Pierisspp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp.,Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp.,Tortrix spp., Trichoplusia ni and Yponomeuta spp.;

from the order Mallophaga, for example,

Damalinea spp. and Trichodectes spp.;

from the order Orthoptera, for example,

Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae,Locusta spp., Periplaneta spp. and Schistocerca spp.;

from the order Psocoptera, for example,

Liposcelis spp.;

from the order Siphonaptera, for example,

Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis;

from the order Thysanoptera, for example,

Frankliniella spp., Hercinothrips spp., Scirtothrips aurantii,Taeniothrips spp., Thrips palmi and Thrips tabaci; and

from the order Thysanura, for example,

Lepisma saccharina.

The active ingredients according to the invention can be used forcontrolling, i.e. containing or destroying, pests of the abovementionedtype which occur in particular on plants, especially on useful plantsand ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of suchplants, and in some cases even plant organs which are formed at a laterpoint in time remain protected against these pests.

Suitable target crops are, in particular, cereals, such as wheat,barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodderbeet; fruit, for example pomaceous fruit, stone fruit or soft fruit,such as apples, pears, plums, peaches, almonds, cherries or berries, forexample strawberries, raspberries or blackberries; leguminous crops,such as beans, lentils, peas or soya; oil crops, such as oilseed rape,mustard, poppies, olives, sunflowers, coconut, castor, cocoa or groundnuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants,such as cotton, flax, hemp or jute; citrus fruit, such as oranges,lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce,asparagus, cabbages, carrots, onions, tomatoes, potatoes or bellpeppers; Lauraceae, such as avocado, Cinnamonium or camphor; and alsotobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines,hops, the plantain family, latex plants and ornamentals.

The active ingredients according to the invention are especiallysuitable for controlling Aphis craccivora, Diabrotica balteata,Heliothis virescens, Myzus persicae, Plutella xylostella and Spodopteralittoralis in cotton, vegetable, maize, rice and soya crops. The activeingredients according to the invention are further especially suitablefor controlling Mamestra (preferably in vegetables), Cydia pomonella(preferably in apples), Empoasca (preferably in vegetables, vineyards),Leptinotarsa (preferably in potatos) and Chilo supressalis (preferablyin rice).

The term “crops” is to be understood as including also crops that havebeen rendered tolerant to herbicides like bromoxynil or classes ofherbicides (such as, for example, HPPD inhibitors, ALS inhibitors, forexample primisulfuron, prosulfuron and trifloxysulfuron, EPSPS(5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS(glutamine synthetase) inhibitors) as a result of conventional methodsof breeding or genetic engineering. An example of a crop that has beenrendered tolerant to imidazolinones, e.g. imazamox, by conventionalmethods of breeding (mutagenesis) is Clearfield® summer rape (Canola).Examples of crops that have been rendered tolerant to herbicides orclasses of herbicides by genetic engineering methods include glyphosate-and glufosinate-resistant maize varieties commercially available underthe trade names RoundupReady® and LibertyLink®.

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising one or more selectively acting toxins,such as are known, for example, from toxin-producing bacteria,especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, forexample, insecticidal proteins, for example insecticidal proteins fromBacillus cereus or Bacillus popliae; or insecticidal proteins fromBacillus thuringiensis, such as δ-endotoxins, e.g. CryIA(b), CryIA(c),CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c, orvegetative insecticidal proteins (VIP), e.g. VIP1, VIP2, VIP3 or VIP3A;or insecticidal proteins of bacteria colonising nematodes, for examplePhotorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens,Xenorhabdus nematophilus; toxins produced by animals, such as scorpiontoxins, arachnid toxins, wasp toxins and other insect-specificneurotoxins; toxins produced by fungi, such as Streptomycetes toxins,plant lectins, such as pea lectins, barley lectins or snowdrop lectins;agglutinins; proteinase inhibitors, such as trypsine inhibitors, serineprotease inhibitors, patatin, cystatin, papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ionchannel blockers, such as blockers of sodium or calcium channels,juvenile hormone esterase, diuretic hormone receptors, stilbenesynthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood byδ-endotoxins, for example CryIA(b), CryIA(c), CryIF, CryIF(a2),CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c, or vegetative insecticidalproteins (VIP), for example VIP1, VIP2, VIP3 or VIP3A, expressly alsohybrid toxins, truncated toxins and modified toxins. Hybrid toxins areproduced recombinantly by a new combination of different domains ofthose proteins (see, for example, WO 02/15701). Truncated toxins, forexample a truncated CryIA(b), are known. In the case of modified toxins,one or more amino acids of the naturally occurring toxin are replaced.In such amino acid replacements, preferably non-naturally presentprotease recognition sequences are inserted into the toxin, such as, forexample, in the case of CryIIIA055, a cathepsin-D-recognition sequenceis inserted into a CryIIIA toxin (see WO 03/018810).

Examples of such toxins or transgenic plants capable of synthesisingsuch toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278,WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processes for the preparation of such transgenic plants aregenerally known to the person skilled in the art and are described, forexample, in the publications mentioned above. CryI-type deoxyribonucleicacids and their preparation are known, for example, from WO 95/34656,EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plantstolerance to harmful insects. Such insects can occur in any taxonomicgroup of insects, but are especially commonly found in the beetles(Coleoptera), two-winged insects (Diptera) and butterflies(Lepidoptera).

Transgenic plants containing one or more genes that code for aninsecticidal resistance and express one or more toxins are known andsome of them are commercially available. Examples of such plants are:YieldGard® (maize variety that expresses a CryIA(b) toxin); YieldGardRootworm® (maize variety that expresses a CryIIIB(b1) toxin); YieldGardPlus® (maize variety that expresses a CryIA(b) and a CryIIIB(b1) toxin);Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I®(maize variety that expresses a CryIF(a2) toxin and the enzymephosphinothricine N-acetyltransferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 33B® (cotton variety thatexpresses a CryIA(c) toxin); Bollgard I® (cotton variety that expressesa CryIA(c) toxin); Bollgard II® (cotton variety that expresses aCryIA(c) and a CryIIA(b) toxin); VIPCOT® (cotton variety that expressesa VIP toxin); NewLeaf® (potato variety that expresses a CryIIIA toxin);NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait),Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a truncated CryIA(b) toxin. Bt11 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.

2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a CryIA(b) toxin. Bt176 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.

3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Maize which hasbeen rendered insect-resistant by transgenic expression of a modifiedCryIIIA toxin. This toxin is Cry3A055 modified by insertion of acathepsin-D-protease recognition sequence. The preparation of suchtransgenic maize plants is described in WO 03/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863expresses a CryIIIB(b1) toxin and has resistance to certain Coleopterainsects.

5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C/NL/00/10. Geneticallymodified maize for the expression of the protein Cry1F for achievingresistance to certain Lepidoptera insects and of the PAT protein forachieving tolerance to the herbicide glufosinate ammonium.

7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue deTervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.Consists of conventionally bred hybrid maize varieties by crossing thegenetically modified varieties NK603 and MON 810. NK603×MON 810 Maizetransgenically expresses the protein CP4 EPSPS, obtained fromAgrobacterium sp. strain CP4, which imparts tolerance to the herbicideRoundup® (contains glyphosate), and also a CryIA(b) toxin obtained fromBacillus thuringiensis subsp. kurstaki which brings about tolerance tocertain Lepidoptera, include the European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS(Zentrum für Biosicherheit and Nachhaltigkeit, Zentrum BATS,Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising antipathogenic substances having aselective action, such as, for example, the so-called“pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392 225).Examples of such antipathogenic substances and transgenic plants capableof synthesising such antipathogenic substances are known, for example,from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191. The methods ofproducing such transgenic plants are generally known to the personskilled in the art and are described, for example, in the publicationsmentioned above.

Antipathogenic substances which can be expressed by such transgenicplants include, for example, ion channel blockers, such as blockers forsodium and calcium channels, for example the viral KP1, KP4 or KP6toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases;the so-called “pathogenesis-related proteins” (PRPs; see e.g. EP-A-0 392225); antipathogenic substances produced by microorganisms, for examplepeptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818)or protein or polypeptide factors involved in plant pathogen defence(so-called “plant disease resistance genes”, as described in WO03/000906).

Further areas of use of the compositions according to the invention arethe protection of stored goods and storerooms and the protection of rawmaterials, such as wood, textiles, floor coverings or buildings, andalso in the hygiene sector, especially the protection of humans,domestic animals and productive livestock against pests of the mentionedtype.

In the hygiene sector, the compositions according to the invention areactive against ectoparasites such as hard ticks, soft ticks, mangemites, harvest mites, flies (biting and licking), parasitic fly larvae,lice, hair lice, bird lice and fleas.

Examples of such parasites are:

Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculusspp. and Phtirus spp., Solenopotes spp.

Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

Of the order Diptera and the suborders Nematocerina and Brachycerina,for example Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp. and Melophagus spp.

Of the order Siphonapterida, for example Pulex spp., Ctenocephalidesspp., Xenopsylla spp., Ceratophyllus spp.

Of the order Heteropterida, for example Cimex spp., Triatoma spp.,Rhodnius spp., Panstrongylus spp.

Of the order Blattarida, for example Blatta orientalis, Periplanetaamericana, Blattelagermanica and Supella spp.

Of the subclass Acaria (Acarida) and the orders Meta- and Meso-stigmata,for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp.,Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp.,Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp.,Pneumonyssus spp., Sternostoma spp. and Varroa spp.

Of the orders Actinedida (Prostigmata) and Acaridida (Astigmata), forexample Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobiaspp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorusspp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp.,Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp.,Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. andLaminosioptes spp.

The compositions according to the invention are also suitable forprotecting against insect infestation in the case of materials such aswood, textiles, plastics, adhesives, glues, paints, paper and card,leather, floor coverings and buildings.

The compositions according to the invention can be used, for example,against the following pests: beetles such as Hylotrupes bajulus,Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum,Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobiumcarpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctuslinearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis,Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychuscapucins, Heterobostrychus brunneus, Sinoxylon spec. and Dinoderusminutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas,Urocerus gigas taignus and Urocerus augur, and termites such asKalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis andCoptotermes formosanus, and bristletails such as Lepisma saccharina.

The invention therefore also relates to pesticidal compositions such asemulsifiable concentrates, suspension concentrates, directly sprayableor dilutable solutions, spreadable pastes, dilute emulsions, solublepowders, dispersible powders, wettable powders, dusts, granules orencapsulations in polymeric substances, which comprise—at least—one ofthe active ingredients according to the invention and which are to beselected to suit the intended aims and the prevailing circumstances.

In these compositions, the active ingredient is employed in pure form, asolid active ingredient for example in a specific particle size, or,preferably, together with—at least—one of the auxiliaries conventionallyused in the art of formulation, such as extenders, for example solventsor solid carriers, or such as surface-active compounds (surfactants).

Examples of suitable solvents are: unhydrogenated or partiallyhydrogenated aromatic hydrocarbons, preferably the fractions C₈ to C₁₂of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes ortetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such asparaffins or cyclohexane, alcohols such as ethanol, propanol or butanol,glycols and their ethers and esters such as propylene glycol,dipropylene glycol ether, ethylene glycol or ethylene glycol monomethylether or ethylene glycol monoethyl ether, ketones, such ascyclohexanone, isophorone or diacetone alcohol, strongly polar solvents,such as N-methylpyrrolid-2-one, dimethyl sulfoxide orN,N-dimethylformamide, water, unepoxidized or epoxidized vegetable oils,such as unexpodized or epoxidized rapeseed, castor, coconut or soya oil,and silicone oils.

Solid carriers which are used for example for dusts and dispersiblepowders are, as a rule, ground natural minerals such as calcite, talc,kaolin, montmorillonite or attapulgite. To improve the physicalproperties, it is also possible to add highly disperse silicas or highlydisperse absorbtive polymers. Suitable particulate adsorptive carriersfor granules are porous types, such as pumice, brick grit, sepiolite orbentonite, and suitable non-sorptive carrier materials are calcite orsand. In addition, a large number of granulated materials of inorganicor organic nature can be used, in particular dolomite or comminutedplant residues.

Suitable surface-active compounds are, depending on the type of theactive ingredient to be formulated, non-ionic, cationic and/or anionicsurfactants or surfactant mixtures which have good emulsifying,dispersing and wetting properties. The surfactants mentioned below areonly to be considered as examples; a large number of further surfactantswhich are conventionally used in the art of formulation and suitableaccording to the invention are described in the relevant literature.

Suitable non-ionic surfactants are, especially, polyglycol etherderivatives of aliphatic or cycloaliphatic alcohols, of saturated orunsaturated fatty acids or of alkyl phenols which may containapproximately 3 to approximately 30 glycol ether groups andapproximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatichydrocarbon radical or approximately 6 to approximately 18 carbon atomsin the alkyl moiety of the alkyl phenols. Also suitable arewater-soluble polyethylene oxide adducts with polypropylene glycol,ethylenediaminopolypropylene glycol or alkyl polypropylene glycol having1 to approximately 10 carbon atoms in the alkyl chain and approximately20 to approximately 250 ethylene glycol ether groups and approximately10 to approximately 100 propylene glycol ether groups. Normally, theabovementioned compounds contain 1 to approximately 5 ethylene glycolunits per propylene glycol unit. Examples which may be mentioned arenonylphenoxypolyethoxyethanol, castor oil polyglycol ether,polypropylene glycol/polyethylene oxide adducts,tributylphenoxypolyethoxyethanol, polyethylene glycol oroctylphenoxypolyethoxyethanol. Also suitable are fatty acid esters ofpolyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are, especially, quarternary ammonium saltswhich generally have at least one alkyl radical of approximately 8 toapproximately 22 C atoms as substituents and as further substituents(unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzylradicals. The salts are preferably in the form of halides,methylsulfates or ethylsulfates. Examples are stearyltrimethylammoniumchloride and benzylbis(2-chloroethyl)ethylammonium bromide.

Examples of suitable anionic surfactants are water-soluble soaps orwater-soluble synthetic surface-active compounds. Examples of suitablesoaps are the alkali, alkaline earth or (unsubstituted or substituted)ammonium salts of fatty acids having approximately 10 to approximately22 C atoms, such as the sodium or potassium salts of oleic or stearicacid, or of natural fatty acid mixtures which are obtainable for examplefrom coconut or tall oil; mention must also be made of the fatty acidmethyl taurates. However, synthetic surfactants are used morefrequently, in particular fatty sulfonates, fatty sulfates, sulfonatedbenzimidazole derivatives or alkylaryl sulfonates. As a rule, the fattysulfonates and fatty sulfates are present as alkali, alkaline earth or(substituted or unsubstituted) ammonium salts and they generally have analkyl radical of approximately 8 to approximately 22 C atoms, alkyl alsoto be understood as including the alkyl moiety of acyl radicals;examples which may be mentioned are the sodium or calcium salts oflignosulfonic acid, of the dodecylsulfuric ester or of a fatty alcoholsulfate mixture prepared from natural fatty acids. This group alsoincludes the salts of the sulfuric esters and sulfonic acids of fattyalcohol/ethylene oxide adducts. The sulfonated benzimidazole derivativespreferably contain 2 sulfonyl groups and a fatty acid radical ofapproximately 8 to approximately 22 C atoms. Examples ofalkylarylsulfonates are the sodium, calcium or triethanolammonium saltsof decylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of anaphthalenesulfonic acid/formaldehyde condensate. Also possible are,furthermore, suitable phosphates, such as salts of the phosphoric esterof a pnonylphenol/(4-14)ethylene oxide adduct, or phospholipids.

As a rule, the compositions comprise 0.1 to 99%, especially 0.1 to 95%,of active ingredient and 1 to 99.9%, especially 5 to 99.9%, of at leastone solid or liquid adjuvant, it being possible as a rule for 0 to 25%,especially 0.1 to 20%, of the composition to be surfactants (% in eachcase meaning percent by weight). Whereas concentrated compositions tendto be preferred for commercial goods, the end consumer as a rule usesdilute compositions which have substantially lower concentrations ofactive ingredient. Preferred compositions are composed in particular asfollows (%=percent by weight):

Emulsifiable Concentrates:

active ingredient: 1 to 95%, preferably 5 to 20% surfactant: 1 to 30%,preferably 10 to 20% solvent: 5 to 98%, preferably 70 to 85%

Dusts:

active ingredient: 0.1 to 10%, preferably 0.1 to 1% solid carrier: 99.9to 90%, preferably 99.9 to 99%

Suspension Concentrates:

active ingredient: 5 to 75%, preferably 10 to 50% water: 94 to 24%,preferably 88 to 30% surfactant: 1 to 40%, preferably 2 to 30%

Wettable Powders:

active ingredient: 0.5 to 90%, preferably 1 to 80% surfactant: 0.5 to20%, preferably 1 to 15% solid carrier: 5 to 99%, preferably 15 to 98%

Granulates:

active ingredient: 0.5 to 30%, preferably 3 to 15% solid carrier: 99.5to 70%, preferably 97 to 85%

PREPARATORY EXAMPLES Example 1 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indole-7-carboxylicacid isopropylamide a) Preparation of 6-amino-1H-indole-7-carboxylicacid methyl ester

This compound is prepared as described in J. Org. Chem., 1996, 61, 1155;LC/MS:191/192 (M+H)⁺.

b) Preparation of 6-amino-1H-indole-7-carboxylic acid

To a solution of 85.2 mg (0.45 mmol) of 6-amino-1H-indole-7-carboxylicacid methyl ester in 4 mL of dioxane and 1 mL of methanol, is added 0.45mL (0.9 mmol) of an aqueous solution of NaOH 2N. The mixture is stirredover the night at 60° C. A new addition of 0.22 mL (0.45 mmol) of anaqueous solution of NaOH 2N is made and the mixture is stirred again 6 hat 60° C. and then cooled to ambient temperature. After evaporation ofall the solvents, a crude yellowish residue is obtained and useddirectly in the next step; ¹H-NMR (MeOD₄, 400 MHz): 7.51 (m, 1H), 7.05(d, 1H), 6.55 (d, 1H), 6.33 (m, 1H) ppm.

c) Preparation of7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazol-3-yl]-1H-8-oxa-1,6-diaza-cyclopenta[a]naphthalen-9-one

To a suspension of 79 mg (0.45 mmol) of 6-amino-1H-indole-7-carboxylicacid in 7 mL of acetonitrile, is added 130 mg (0.45 mmol) of2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carboxylicacid followed by 0.16 mL (2.06 mmol) of pyridine. The mixture is stirredat ambient temperature during 30 minutes. Then the suspension is cooledto 0° C. and 0.12 mL (1.57 mmol) of methanesulfonyl chloride is addeddropwise. The mixture is stirred at 0° C. during 30 minutes and 2 hoursat ambient temperature. After evaporation of the solvent, the residue istriturated with a minimum of cold water. The precipitate which is formedis filtrated and washed with cold water. The residue is then purified bycolumn chromatography on silica gel with hexanes and ethyl acetate aseluents and 47.1 mg (0.11 mmol, 25%) of a yellowish solid are obtained;LC/MS:432/434 (M+H)⁺.

d) Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indole-7-carboxylicacid isopropylamide

To a solution of 110 mg (0.25 mmol) of the crude7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazol-3-yl]-1H-8-oxa-1,6-diaza-cyclopenta[a]naphthalen-9-onein 2.5 mL of anhydrous tetrahydrofuran, under Argon, is added 0.07 mL(0.77 mmol) of isopropylamine. The reaction is stirred during 5 hours atambient temperature and then quenched with an aqueous saturated solutionof ammonium chloride. The product is extracted twice with ethyl acetateand the combined organic phases are dried on Na₂SO₄, filtrated and thesolvent is evaporated. After purification by flash chromatography onsilica gel with hexanes and ethyl acetate as eluents and a preparativethin layer chromatography, 18.5 mg (0.04 mmol, 16%) of a white solid areobtained; LC/MS:513/515 (M+Na)⁺, m.p.: 240-242° C.

Example 2 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indole-7-carboxylicacid cyclopropylamide

See step d of example 1 with7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazol-3-yl]-1H-8-oxa-1,6-diaza-cyclopenta[a]naphthalen-9-oneas starting material and cyclopropanemethylamine. After 3 hours ofreaction, work-up and column chromatography purification, a white powderis obtained (75%); LC/MS:525/527 (M+Na)⁺, m.p.: 239-241° C.

Example 3 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid isopropylamide a) Preparation of1,6-dihydro-pyrrolo[2,3-g]indazole-7,8-dione

This compound is prepared as described in Tet. Lett., 1980, 21, 3029;LC/MS:188/189 (M+H)⁺.

b) Preparation of 6-amino-1H-indazole-7-carboxylic acid

This compound is prepared as described in J. Org. Chem., 2000, 65, 4193using 1,6-dihydro-pyrrolo[2,3-g]indazole-7,8-dione as starting material;LC/MS:178/179 (M+H)⁺.

c) Preparation of7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-one

See step c example 1 with 6-amino-1H-indazole-7-carboxylic acid asstarting material. After overnight reaction, work-up and columnchromatography purification on silica gel with hexanes and ethyl acetateas eluents, a yellowish solid is obtained (63%); LC/MS:433/435 (M+H)⁺.

d) Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-indazole-7-carboxylicacid isopropylamide

See step d example 1 with7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-oneas starting material. After overnight reaction and column chromatographypurification on silica gel with hexanes and ethyl acetate as eluents, aslightly beige solid is obtained (72%); LC/MS:492/494 (M+H)⁺, m.p.:203-205° C.

Example 4 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid cyclopropylmethyl-amide

See example 2 with7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-oneas starting material. After overnight reaction and column chromatographypurification on silica gel with hexanes and ethyl acetate as eluents, aslightly beige solid is obtained (77%); LC/MS:504/506 (M+H)⁺, m.p.:240-242° C.

Example 5 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid bicyclopropyl-1-ylamide

See step d in example 1 with7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-oneas starting material. The reaction is performed with 1.5 equivalents ofbicyclopropyl-1-ylamine hydrochloride and triethylamine. After overnightreaction at ambient temperature, 0.3 equivalents of the amine and thebase are added and the reaction is stirred overnight at 50° C. Aftercolumn chromatography purification on silica gel with hexanes and ethylacetate as eluents, a yellowish solid is obtained (70%); LC/MS:530/532(M+H)⁺, m.p.: 224-227° C.

Example 6 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid methylamide

This compound is prepared as described in step d in example 1 with7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-oneas starting material and 2 equivalents of methylamine (40% in water).After overnight reaction at ambient temperature, the mixture isevaporated and submitted to column chromatography purification withhexanes and ethyl acetate as eluents. A slightly beige solid is obtained(96%); LC/MS:464/466 (M+H)⁺, m.p.: 190-192° C.

Example 7 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid (1,1-dimethyl-2-methylsulfanyl-ethyl)-amide

To a mixture of 200 mg (0.46 mmol) of7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-onein 4 mL of anhydrous tetrahydrofuran is added 110 mg (0.92 mmol) of1,1-dimethyl-2-methylsulfanylethylamine. The mixture is stirredovernight at ambient temperature, then 3 days at 50° C. Then 55 mg (0.46mmol) of the amine is added again and the mixture is stirred overnightat 65° C. After column chromatography purification on silica gel withhexanes and ethyl acetate, a slightly beige solid (169 mg, 0.31 mmol,66%) are obtained after evaporation; LC/MS: 552/554 (M+H)⁺, m.p.:100-105° C.

Example 8 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid (2-methanesulfinyl-1,1-dimethyl-ethyl)-amide

To a mixture of 144 mg (0.26 mmol) of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid (1,1-dimethyl-2-methylsulfanylethyl)-amide, prepared in example 7in 2.88 mL of methylene chloride at 0° C. is added dropwise 64 mg (0.26mmol) of m-chloroperbenzoic acid dissolved in 0.5 mL of methylenechloride. The mixture is stirred and let warm-up to ambient temperaturewithin 1 hour. The reaction is quenched by the addition of an aqueoussaturated sodium carbonate solution. The product is extracted with ethylacetate (3 times) and the combined organic extracts are dried on Na₂SO₄,filtrated and evaporated. After a flash chromatography with hexanes andethyl acetate as eluents, 111 mg (0.17 mmol, 75%) of a white solid areobtained; LC/MS: 568/570 (M+H)⁺.

Example 9 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid (2-methanesulfonyl-1,1-dimethyl-ethyl)amide

See example 8 for the preparation of this compound using6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid (1,1-dimethyl-2-methylsulfanyl-ethyl)-amide, prepared as in example7, as starting material and 2 equivalents of m-chloroperbenzoic acid.After 30 minutes of stirring at ambient temperature under nitrogen, thereaction is quenched as described previously. After flash chromatographyon silica gel with hexanes and ethyl acetate as eluents, a yellowishsolid is obtained (67%); LC/MS:584/586 (M+H)⁺.

Example 10 Preparation of5-chloro-6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid isopropylamide a) Preparation of 6-amino-1H-indazole-7-carboxylicacid methyl ester

This compound is prepared as described in Angew. Chem. Int. Ed. Engl.,1981, 20, 882 using 6-dihydro-pyrrolo[2,3-g]indazole-7,8-dione, preparedin step a example 3, as starting material; LC/MS:192/193 (M+H)⁺.

b) Preparation of 6-amino-5-chloro-1H-indazole-7-carboxylic acid methylester

To a mixture of 1.66 g (8.71 mmol) of 6-amino-1H-indazole-7-carboxylicacid methyl ester in 17 mL of N,N-dimethylformamide, is added 1.21 g(8.71 mmol) of N-chlorosuccinimide. The mixture is stirred during 4hours at 50° C. and then the solvent is evaporated. The residue isprecipitated in ethyl acetate and after filtration and washings withethyl acetate, 927 mg of a pure white solid are obtained. The filtrateis evaporated and submitted to a flash chromatography which gives anadditional 723 mg of the compound. In totality, 1.65 g (84%) of aproduct are obtained as a white solid; LC/MS:226/228 (M+H)⁺.

c) Preparation of 6-amino-5-chloro-1H-indazole-7-carboxylic acid

See step b example 1 for the preparation of this compound using6-amino-5-chloro-1H-indazole-7-carboxylic acid methyl ester as startingmaterial. The reaction is stirred 6 hours at 50° C. Then afterevaporation, the residue is dissolved in a minimum of water and the pHof the mixture is adjusted to 2 with an aqueous solution of HCl 1N. Thewhite precipitate, which is formed is filtrated and washed with aminimum of water. A white solid is obtained (96%); LC/MS:212/214 (M+H)⁺.

d) Preparation of5-chloro-7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-one

See step c example 1 with 6-amino-5-chloro-1H-indazole-7-carboxylic acidas starting material. After overnight reaction at ambient temperature,work-up and a column chromatography purification on silica gel withhexanes and ethyl acetate as eluents affords the product (39%) as ayellowish solid; LC/MS:467/469 (M+H)⁺.

e) Preparation of5-chloro-6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid isopropylamide

See step d example 1 with5-chloro-7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-oneas starting material. After overnight reaction and flash columnchromatography purification a slightly beige solid is obtained (44%);LC/MS:526/528 (M+H)⁺, m.p.: 245-247° C.

Example 11 Preparation of5-chloro-6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid cyclopropylmethyl-amide

See example 2 with5-chloro-7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-oneas starting material with 2 equivalents of cyclopropanemethylamine and1.5 equivalents of triethylamine. The reaction is stirred over the nightat ambient temperature and after a flash chromatography, a white solidis obtained (43%); LC/MS:538/540 (M+H)⁺, m.p.: >250° C.

Example 12 Preparation of5-chloro-6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid bicyclopropyl-1-ylamide

This compound is prepared as described in step d example 1 with5-chloro-7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-oneas starting material. The reaction is performed with 2 equivalents ofbicyclopropyl-1-ylamine hydrochloride and triethylamine. After overnightstirring at ambient temperature, 0.3 equivalents of amine and base areadded and the mixture is stirred again overnight at 50° C. After work-upand flash chromatography, a white solid is obtained (62%); LC/MS:564/566(M+H)⁺, m.p.: >250° C.

Example 13 Preparation of5-chloro-6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid (1,1-dimethyl-2-methylsulfanylethyl)-amide

This compound is prepared as in example 7 with5-chloro-7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-one,prepared in step d in example 10, as starting material and 2.5equivalents of 1,1-dimethyl-2-methylsulfanyl-ethylamine. The reaction isstirred during 2 days at 65° C. and then 1 more equivalent of amine isadded. The reaction is stirred for a further 2 days at 65° C. Afterwork-up and flash chromatography purification, a yellowish solid isobtained (56%); LC/MS:586/588 (M+H)⁺, m.p.: 100-105° C.

Example 14 Preparation of5-chloro-6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid (2-methanesulfinyl-1,1-dimethylethyl)-amide

See example 8 for the preparation of this compound starting from5-chloro-6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid (1,1-dimethyl-2-methylsulfanyl-ethyl)-amide, prepared in example13. After 1 hour of reaction, work-up as described before and columnchromatography purification, a yellowish solid is obtained (80%);LC/MS:602/604 (M+H)⁺, 624/626 (M+Na)⁺.

Example 15 Preparation of5-chloro-6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid (2-methanesulfonyl-1,1-dimethylethyl)-amide

This compound is prepared as described in example 9 with5-chloro-6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid (1,1-dimethyl-2-methylsulfanyl-ethyl)-amide as starting material,prepared in example 13, with 2 equivalents of m-chloroperbenzoic acid.After 30 minutes of stirring at ambient temperature under nitrogen, thereaction is quenched as described previously. After flash chromatographyon silica gel with hexanes and ethyl acetate as eluents, a yellowishsolid is obtained (57%); LC/MS:640/642 (M+Na)⁺, m.p.: 173-176° C.

Example 16 Preparation of5-bromo-6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid isopropylamide a) Preparation of6-amino-5-bromo-1H-indazole-7-carboxylic acid methyl ester

To a mixture of 3.4 g (17.78 mmol) of 6-amino-1H-indazole-7-carboxylicacid methyl ester, prepared as in step a in example 10, in 34 mL ofN,N-dimethylformamide is added 3.16 g (17.78 mmol) ofN-bromosuccinimide. The reaction is stirred at ambient temperature 4hours. After concentration in vacuo the residue is triturated in ethylacetate and after filtration 3.38 g of a brownish solid are obtained.The filtrate is evaporated and submitted to column chromatographypurification on silica gel with hexanes and ethyl acetate as eluents toafford 563 mg of a white solid. In totality 3.95 g (82%) of a productare obtained; LC/MS:270/272 (M+H)⁺.

b) Preparation of 6-amino-5-bromo-1H-indazole-7-carboxylic acid

See step b example 1 for the preparation of this compound with6-amino-5-bromo-1H-indazole-7-carboxylic acid methyl ester as startingmaterial. After overnight reaction at 50° C., the solvent is evaporatedand the product is precipitated with an aqueous solution of HCl 1N. Thesolid obtained is filtered and washed with a minimum of water. The crudewhite solid obtained is used directly in the next step; LC-MS: 256/258(M+H)⁺.

c) Preparation of5-bromo-7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-one

See step c in example 1 for the preparation of this compound with6-amino-5-bromo-1H-indazole-7-carboxylic acid as starting material. Thereaction is stirred for 30 minutes at 0° C. and then overnight atambient temperature. After concentration in vacuo, the residue isprecipitated with a minimum of water and filtrated. Columnchromatography purification on silica gel with hexanes and ethyl acetateas eluents affords the product (51%) as a yellow solid; LC/MS:511/513(M+H)⁺.

d) Preparation of5-bromo-6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid isopropylamide

This compound is prepared as described in step d in example 1 with5-bromo-7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-oneas starting material. The reaction is performed with 3 equivalents ofisopropylamine and the reaction mixture is stirred at ambienttemperature overnight. After column chromatography purification, a whitesolid is obtained (57%); LC/MS: 570/572 (M+H)⁺, m.p.: 189-190° C.

Example 17 Preparation of5-bromo-6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid methylamide

This compound is prepared as described in step d in example 1 with5-bromo-7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-oneas starting material and 3 equivalents of an aqueous solution ofmethylamine (40%). After overnight reaction at ambient temperature andpurification by column chromatography on silica gel with hexanes andethyl acetate as eluents, a white solid is obtained (59%); LC/MS:564/566(M+Na)⁺, m.p: >255° C.

Example 18 Preparation of5-bromo-6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid bicyclopropyl-1-ylamide

This compound is prepared as described in step d of example 1 with5-bromo-7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-oneas starting material, 3 equivalents of bicyclopropyl-1-ylaminehydrochloride and 3 equivalents of triethylamine. After overnightreaction at ambient temperature, the mixture is warmed at 50° C. andstirred again during overnight, then 2 equivalents of amine andtriethylamine are added and the reaction is stirred at 50° C. during 24hours. After flash chromatography purification, a yellowish solid isobtained (53%); LC/MS:608/610 (M+H)⁺, m.p.: 212-214° C.

Example 19 Preparation of5-bromo-6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid cyclopropylmethyl-amide

See example 2 for the preparation of this compound with5-bromo-7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-oneas starting material and 3 equivalents of cyclopropanemethylamine. Afterovernight reaction at ambient temperature and flash chromatography withhexanes and ethyl acetate as eluents, a yellowish solid is obtained(72%); LC/MS:582/584 (M+H)⁺, m.p.: 144-150° C.

Example 20 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-2,7-dimethyl-quinoline-5-carboxylicacid isopropylamide

1.70 g (3.53 mMol)N-(4-amino-2-methyl-6-(((1-methylethyl)amino)carbonyl)phenyl)-1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1H-pyrazole-5-carboxamide(known from WO 03/016284) and 41 mg (0.18 mmol) benzyltriethylammoniumchloride in 35 mL conc. HCl and 35 mL toluene are vigorously stirred at60° C. Then 0.58 mL (7 mmol) crotonaldehyde is added and the reactionmixture is stirred under reflux during 1 hour. The mixture is thencooled to ambient temperature, diluted with 10 mL ethylacetate/tetrahydrofuran (1:1, v/v) and neutralised with an aqueoussolution of concentrated ammonia. The organic phase is extracted andwashed once with brine, then dried on Na₂SO₄, filtrated and evaporated.After column chromatography purification on silica gel withdichloromethane/tetrahydrofuran (3:1) as eluents, the compound isrecrystallised from tetrahydrofuran/hexane to afford a colourless solid;LC/MS:531/533 (M+H)⁺, m.p.: >240° C.

Example 21 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-2,7-dimethyl-quinoline-1-oxy-5-carboxylicacid isopropylamide

To 530 mg (1.0 mmol)6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-2,7-dimethyl-quinoline-5-carboxylicacid isopropylamide prepared in example 20 in 25 mL dichloroethane, isadded 380 mg (4.0 mMol) urea hydrogen peroxide addition compound and0.31 mL trifluoroacetic acid. The mixture is stirred at 40° C. during 72hours. After evaporation of the solvent, ethyl acetate is added and themixture is washed with brine, dried and the solvent evaporated.Filtration of the residue over silica gel (eluent:tetrahydrofuran/hexane=2:1) gives a colourless solid, which isrecrystallised from dichloromethane/hexane; LC/MS:547/549 (M+H)⁺,m.p.: >230° C.

Example 22 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-2,7-dimethyl-quinoline-5-carboxylicacid methylamide

See example 20 for the preparation of this compound fromN-(4-amino-2-methyl-6-(((1-methyl)amino)carbonyl)phenyl)-1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1H-pyrazole-5-carboxamide.After chromatography on silica gel (eluent: tetrahydrofuran/hexane=1:1)a colourless solid is obtained; m.p.: >134° C.

Example 23 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-2,7-dimethyl-quinoline-5-carboxylicacid ethylamide

See example 20 for the preparation of this compound fromN-(4-amino-2-methyl-6-(((1-ethyl)amino)carbonyl)phenyl)-1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1H-pyrazole-5-carboxamide.After chromatography on silica gel (eluent: THF/hexane=1:1) a colourlesssolid is obtained; LC/MS:517/519 (M+H)⁺, m.p.: >230° C.

Example 24 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-3-ethyl-7-methyl-2-propyl-quinoline-5-carboxylicacid isopropylamide

0.48 g (1.0 mMol)N-(4-amino-2-methyl-6-(((1-methylethyl)amino)carbonyl)phenyl)-1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1H-pyrazole-5-carboxamide(known from WO 03/016284), 0.27 mL (3.0 mMol) butyraldehyde and 31 mg(0.05 mMol) ytterbium(III) trifluoromethanesulfonate in 20 mLdimethylsulfoxide are stirred at 100° C. during 24 hours. After coolingthe mixture is diluted with ethyl acetate, washed with brine, dried andthe solvent evaporated. Chromatography of the residue on silica gel(eluent: ethyl acetate/hexane=1:1) gives a colourless solid, which isrecrystallised from dichloromethane/hexane; LC/MS:587/589 (M+H)⁺, m.p.213-220° C.

Example 25 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-5-cyano-1H-indazole-7-carboxylicacid isopropylamide a) Preparation of6-amino-5-cyano-1H-indazole-7-carboxylic acid methyl ester

To a solution of 500 mg (1.85 mmol) of6-amino-5-bromo-1H-indazole-7-carboxylic acid methyl ester, prepared asin step a in example 16, in 10 mL of N,N-dimethylformamide under anatmosphere of argon is added 135 mg (1.15 mmol) of zinc cyanide and 206mg (0.185 mmol) of tetrakis(triphenylphsophine)palladium. The reactionmixture is stirred in a microwave oven at 180° C. for 5 minutes. Then, a1:1 v/v mixture of ethyl acetate and tertbutylmethyl ether and brine areadded to the reaction and the phases are separated. The aqueous layer isextracted with tert-butylmethylether. The organic extracts are washedtwice with brine, dried over MgSO₄ and concentrated in vacuo. Theresidue is purified by flash chromatography (SiO₂, hexane/ethyl acetate2:1 to 1:1, gradient) to afford 380 mg of product (94%) as a yellowishsolid; LC/MS:217/218 (M+H)⁺.

b) Preparation of 6-amino-5-cyano-1H-indazole-7-carboxylic acid

See step b example 1 for the preparation of this compound with6-amino-5-cyano-1H-indazole-7-carboxylic acid methyl ester as startingmaterial. After 5 hours of reaction time at ambient temperature, thesolvents are evaporated and water is added to the residue. The productis precipitated at pH 3 by addition of 1N aqueous HCl, filtrated, washedwith a minimum of water and dried by azeotropic distillation withtoluene. The yellowish solid (90%) obtained is used directly in the nextstep; LC/MS: 203 (M+H)⁺.

c) Preparation of7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazol-3-yl]-9-oxo-1,9-dihydro-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalene-5-carbonitrile

See step c in example 1 for the preparation of this compound with6-amino-5-cyano-1H-indazole-7-carboxylic acid as starting material. Thereaction mixture is stirred at 50° C. for 16 hours and then concentratedin vacuo. The solid residue is triturated with a minimum of water andfiltrated. The yellow solid isolated is dried and engaged in the nextstep; LC/MS: 458/460 (M+H)⁺.

d) Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-5-cyano-1H-indazole-7-carboxylicacid isopropylamide

To a mixture of 600 mg of the above7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazol-3-yl]-9-oxo-1,9-dihydro-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalene-5-carbonitrilein 5 mL of acetonitrile/water (4:1, v/v) is added 1.1 mL (12.9 mmol) ofisopropylamine. The reaction mixture is stirred during 4 hours atambient temperature and then concentrated in vacuo. After purificationby flash chromatography (SiO₂, hexanes/ethyl acetate 4:1), 250 mg (38%)of a white solid are obtained; LC/MS:518/520 (M+H)⁺.

Example 26 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-5-cyano-1H-indazole-7-carboxylicacid bicyclopropyl-1-ylamide

To a solution of 500 mg of the above7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazol-3-yl]-9-oxo-1,9-dihydro-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalene-5-carbonitrilein 8 mL of N,N-dimethylformamide is added 218 mg (1.63 mmol) ofbicyclopropyl-1-ylamine hydrochloride and 303 μL (2.18 mmol) oftriethylamine. The reaction is stirred at 60° C. for 24 hours and thenconcentrated in vacuo. The residue is taken-up with water and ethylacetate. The phases are separated and the aqueous layer is washed withethyl acetate. The combined organic layers are washed several times withbrine, dried over MgSO₄ and concentrated in vacuo. Purification of theresidue by flash chromatography (SiO₂, hexanes/ethyl acetate 3:9)affords 76 mg (12% over two steps) of the product as white solid; LC/MS:555/557 (M+H)⁺.

Example 27 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazole-3-carbonyl]-amino}-5-methyl-1H-indazole-7-carboxylicacid isopropylamide a) Preparation of6-amino-5-methyl-1H-indazole-7-carboxylic acid methyl ester

To a solution of 500 mg (1.85 mmol) of6-amino-5-bromo-1H-indazole-7-carboxylic acid methyl ester, prepared asin step a in example 16, in 10 mL of dioxane under an atmosphere ofargon is added 767 mg (5.55 mmol) of K₂CO₃, 106 mg (0.09 mmol) oftetrakis(triphenylphsophine)palladium and 232 mg (1.85 mmol) oftrimethylboroxine. The reaction mixture is stirred in a microwave ovenat 180° C. for 5 minutes. After filtration over Celite and concentrationin vacuo, the residue is purified sequentially by flash chromatography(SiO₂, hexanes/ethyl acetate 6:4) and reverse phase chromatography toafford 163 mg of product (43% over two steps) as a pale yellowish solid;LC/MS:206/207 (M+H)⁺.

b) Preparation of 6-amino-5-methyl-1H-indazole-7-carboxylic acid

See step b example 1 for the preparation of this compound with6-amino-5-methyl-1H-indazole-7-carboxylic acid methyl ester as startingmaterial. After 24 h of reaction time at ambient temperature, thesolvents are evaporated and water is added to the residue. The productis precipitated at pH 3 by addition of 1N aqueous HCl, filtrated, washedwith a minimum of water and dried by azeotropic distillation withtoluene. The yellowish solid (91%) obtained is used directly in the nextstep; LC/MS:5192/193 (M+H)⁺.

c) Preparation of7-[2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazol-3-yl]-5-methyl-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-one

See step c in example 1 for the preparation of this compound with6-amino-5-methyl-1H-indazole-7-carboxylic acid as starting material. Thereaction mixture is stirred at ambient temperature for 16 hours and thenconcentrated in vacuo. The solid residue is triturated with a minimum ofwater and filtrated. The yellowish solid isolated is dried and engagedin the next step; LC/MS:409/411 (M+H)⁺.

d) Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazole-3-carbonyl]-amino}-5-methyl-1H-indazole-7-carboxylicacid isopropylamide

To a mixture of 500 mg of the above7-[2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazol-3-yl]-5-methyl-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-onein 10 mL of 4:1 (v/v) mixture of acetonitrile/water is added 1.0 mL(12.2 mmol) of isopropylamine. The reaction mixture is stirred during 1hour at ambient temperature and for 2.5 hours at 60° C. and thenconcentrated in vacuo. The residue is taken-up with brine andtert-butylmethylether. The phases are separated and the aqueous layer iswashed with tert-butylmethylether. The combined organic layers arewashed with brine, dried over MgSO₄ and concentrated in vacuo.Purification of the residue by flash chromatography (SiO₂, hexanes/ethylacetate 3:7) affords 118 mg (19% over two steps) of the product as whitesolid; LC/MS:468/470 (M+H)⁺, m.p.: 148-151° C.

Example 28 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazole-3-carbonyl]-amino}-5-methyl-1H-indazole-7-carboxylicacid bicyclopropyl-1-ylamide

To a solution of 500 mg of the above7-[2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazol-3-yl]-5-methyl-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-onein 8 mL of N,N-dimethylformamide is added 244 mg (1.83 mmol) ofbicyclopropyl-1-ylamine hydrochloride and 340 μL (2.44 mmol) oftriethylamine. The reaction is stirred at 70° C. for 16 hours and thenconcentrated in vacuo. The residue is taken-up with water and ethylacetate. The phases are separated and the aqueous layer is washed withethyl acetate. The combined organic layers are washed several times withbrine, dried over MgSO₄ and concentrated in vacuo. Purification of theresidue by flash chromatography (SiO₂, hexanes/ethyl acetate 3:7)affords 90 mg (15% over two steps) of product as a pale yellowish solid;LC/MS:506/508 (M+H)⁺, m.p.: 150-154° C.

Example 29 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-(2,2,2-trifluoro-ethoxy)-2H-pyrazole-3-carbonyl]-amino}-5-methyl-1H-indazole-7-carboxylicacid isopropylamide a) Preparation of7-[2-(3-chloro-pyridin-2-yl)-5-(2,2,2-trifluoro-ethoxy)-2H-pyrazol-3-yl]-5-methyl-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-one

To a suspension of 500 mg (2.61 mmol) of6-amino-5-methyl-1H-indazole-7-carboxylic acid in 20 mL of anhydroustetrahydrofuran is added 790 mg (2.61 mmol) of2-(3-chloro-pyridin-2-yl)-5-(2,2,2-trifluoro-ethoxy)-2H-pyrazole-3-carboxylicacid followed by 945 μL (11.7 mmol) of pyridine. The mixture is stirredat ambient temperature during 30 minutes. Then the suspension is cooledto 0° C. and 708 μL (9.1 mmol) of methanesulfonyl chloride are addeddropwise. The mixture is stirred at 50° C. for 16 hours. Then thesolvent is evaporated and the residue is triturated with a minimum ofcold water. The precipitate, which is formed is filtrated and washedwith cold water. The pale yellowish product obtained (1.0 g) is engagedin the next step: LC/MS:477/479 (M+H)⁺.

b) Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-(2,2,2-trifluoro-ethoxy)-2H-pyrazole-3-carbonyl]-amino}-5-methyl-1H-indazole-7-carboxylicacid isopropylamide

To a suspension of 500 mg of the above7-[2-(3-chloro-pyridin-2-yl)-5-(2,2,2-trifluoro-ethoxy)-2H-pyrazol-3-yl]-5-methyl-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-onein 10 mL of acetonitrile/water (4:1, v/v) is added 885 μL (10.4 mmol) ofisopropylamine. The reaction mixture is stirred for 16 hours at ambienttemperature and then concentrated in vacuo. The residue is taken-up withbrine and ethyl acetate. The phases are separated and the aqueous layeris washed with ethyl acetate. The combined organic layers are washedwith brine, dried over MgSO₄ and concentrated in vacuo. Purification ofthe residue by flash chromatography (SiO₂, hexane/ethyl acetate 4:6)affords 60 mg (10% over two steps) of the product as a white solid;LC/MS:536/538 (M+H)⁺, m.p.: 247-250° C.

Example 306-{[2-(3-chloro-pyridin-2-yl)-5-(2,2,2-trifluoro-ethoxy)-2H-pyrazole-3-carbonyl]-amino}-5-methyl-1H-indazole-7-carboxylicacid bicyclopropyl-1-ylamide

See example 28 for the preparation of this compound with7-[2-(3-chloro-pyridin-2-yl)-5-(2,2,2-trifluoro-ethoxy)-2H-pyrazol-3-yl]-5-methyl-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-oneas the starting material. The reaction is stirred at 60° C. for 24 hoursand then concentrated in vacuo. The residue is taken-up with water andethyl acetate. The phases are separated and the aqueous layer is washedwith ethyl acetate. The combined organic layers are washed several timeswith brine, dried over MgSO₄ and concentrated in vacuo. Purification ofthe residue by flash chromatography (SiO₂, hexane/ethyl acetate 3:7)affords 75 mg (10% over two steps) of the product as a white solid;LC/MS:574/576 (M+H)⁺, m.p.: 240-242° C.

Example 31 Preparation of6-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-5-methyl-1H-indazole-7-carboxylicacid isopropylamide a) Preparation of7-[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazol-3-yl]-5-methyl-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-one

To a suspension of 700 mg (3.66 mmol) of6-amino-5-methyl-1H-indazole-7-carboxylic acid in 26 mL of anhydrousacetonitrile is added 1.11 g (3.66 mmol) of5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid followedby 1.3 mL (16.2 mmol) of pyridine. The mixture is stirred at ambienttemperature during 30 minutes. Then the suspension is cooled to 0° C.and 1.0 mL (12.9 mmol) of methanesulfonyl chloride is added drop wise.The mixture is stirred at ambient temperature for 16 hours. Then thesolvent is evaporated and the residue is triturated with a minimum ofcold water. The precipitate, which is formed is filtrated, washed withcold water and dried. The pale yellowish product obtained (1.6 g) isengaged in the next step; LC/MS:459/461 (M+H)⁺.

b) Preparation of6-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-5-methyl-1H-indazole-7-carboxylicacid isopropylamide

To a suspension of 600 mg of the above7-[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazol-3-yl]-5-methyl-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-onein 10 mL of acetonitrile/water (4:1, v/v) is added 1.11 mL (13.1 mmol)of isopropylamine. The reaction mixture is stirred for 9 hours atambient temperature and then concentrated in vacuo. The residue istaken-up with brine and ethyl acetate. The phases are separated and theaqueous layer is washed with ethyl acetate. The combined organic layersare washed with brine, dried over MgSO₄ and concentrated in vacuo.Purification of the residue by flash chromatography (SiO₂, hexane/ethylacetate 1:2) affords 110 mg (16% over two steps) of the product as awhite solid; LC/MS:518/520 (M+H)⁺, m.p.: 163-166° C.

Example 32 Preparation of6-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-5-methyl-1H-indazole-7-carboxylicacid bicyclopropyl-1-ylamide

See example 28 for the preparation of this compound with7-[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazol-3-yl]-5-methyl-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-oneas the starting material. The reaction is stirred at 50° C. for 27 hoursand then concentrated in vacuo. Purification of the residue by flashchromatography (SiO₂, hexane/ethyl acetate 1:2) and crystallisation inhexanes affords 20 mg (5% over two steps) of the product as a whitesolid; LC/MS:556/558 (M+H)⁺, m.p.: 170-173° C.

Example 33 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-difluoromethyl-2H-pyrazole-3-carbonyl]-amino}-5-methyl-1H-indazole-7-carboxylicacid isopropylamide a) Preparation of7-[2-(3-chloro-pyridin-2-yl)-5-difluoromethyl-2H-pyrazol-3-yl]-5-methyl-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-one

To a suspension of 540 mg (2.82 mmol) of6-amino-5-methyl-1H-indazole-7-carboxylic acid in 20 mL of anhydrousacetonitrile is added 771 mg (2.82 mmol) of2-(3-chloro-pyridin-2-yl)-5-difluoromethyl-2H-pyrazole-3-carboxylic acidfollowed by 1.02 mL (12.7 mmol) of pyridine. The mixture is stirred atambient temperature during 30 minutes. Then the suspension is cooled to0° C. and 766 μL (9.9 mmol) of methanesulfonyl chloride is addeddropwise. The mixture is stirred at 50° C. for 16 hours. Then thesolvent is evaporated and the residue is triturated with a minimum ofcold water. The precipitate, which is formed is filtrated, washed withcold water and dried. The pale yellowish product obtained is engaged inthe next step; LC/MS:429/431 (M+H)⁺.

b) Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-difluoromethyl-2H-pyrazole-3-carbonyl]-amino}-5-methyl-1H-indazole-7-carboxylicacid isopropylamide

To a suspension of 600 mg of the above7-[2-(3-chloro-pyridin-2-yl)-5-difluoromethyl-2H-pyrazol-3-yl]-5-methyl-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-onein 10 mL of acetonitrile/water (4:1, v/v), is added 1.2 mL (14.0 mmol)of isopropylamine. The reaction mixture is stirred for 6 hours atambient temperature and then concentrated in vacuo. The residue istaken-up with brine and ethyl acetate. The phases are separated and theaqueous layer is washed with ethyl acetate. The combined organic layersare washed with brine, dried over MgSO₄ and concentrated in vacuo.Trituration of the residue in ethyl acetate affords 106 mg (15% over twosteps) of the product as a pale yellowish solid; LC/MS:488/490 (M+H)⁺;m.p.: 250-253° C.

Example 34 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-5-ethynyl-1H-indazole-7-carboxylicacid isopropylamide a) Preparation of6-amino-5-trimethylsilanylethynyl-1H-indazole-7-carboxylic acid methylester

To a solution of 1.5 g (5.6 mmol) of6-amino-5-bromo-1H-indazole-7-carboxylic acid methyl ester, prepared asin step a in example 16, in 3 mL of N,N-dimethylformamide under anatmosphere of argon is added 785 μL (5.6 mmol) oftrimethylsilylacetylene, 8.65 mL of diethylamine (83.2 mmol), 194 mg(0.28 mmol) of dichlorobis(triphenylphosphine)palladium II and 53 mg(0.28 mmol) of copper iodide. The reaction mixture is stirred in amicrowave oven at 150° C. for 5 minutes, filtrated over Celite (washingwith ethyl actetate) and concentrated in vacuo. The residue is purifiedby flash chromatography (SiO₂, hexane/ethyl acetate 2:1) to afford 970mg of the product (61%) as a yellowish solid; LC/MS:288/289 (M+H)⁺.

b) Preparation of 6-amino-5-ethynyl-1H-indazole-7-carboxylic acid methylester

To a solution of 500 mg (1.74 mmol) of6-amino-5-trimethylsilanylethynyl-1H-indazole-7-carboxylic acid methylester in 17 mL of anhydrous tetrahydrofuran under an atmosphere of argonis added 2.6 mL (2.6 mmol) of a 1 M solution tetrabutylamonium fluoridein tetrahydrofuran. The reaction mixture is stirred at ambienttemperature for 2 hours. Water and tert-butylmethylether are added andthe two phases are separated. The aqueous layer is extracted withtert-butylmethylether. The combined organic extracts are washed withbrine, dried over MgSO₄ and concentrated in vacuo. The residue issuspended in hexanes. Filtration affords 210 mg (56%) of the product asa yellowish solid; LC/MS:216/217 (M+H)⁺.

c) Preparation of 6-amino-5-ethynyl-1H-indazole-7-carboxylic acid

To a solution of 200 mg (0.93 mmol) of6-amino-5-ethynyl-1H-indazole-7-carboxylic acid methyl ester in 4.2 mLof dioxane and 0.2 mL of methanol is added 2.3 mL (2.3 mmol) of a 1Naqueous solution of NaOH. The mixture is stirred for 5 hours at 50° C.The solvents are evaporated and water is added to the residue. Theproduct is precipitated at pH 4 by addition of 1N aqueous HCl,filtrated, washed with a minimum of water and dried by azeotropicdistillation with toluene. The yellowish solid obtained is used directlyin the next step; LC/MS: 202/203 (M+H)⁺.

d) Preparation of7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazol-3-yl]-5-ethynyl-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-one

To a suspension of 200 mg (0.99 mmol) of6-amino-5-ethynyl-1H-indazole-7-carboxylic acid in 7 mL of anhydrousacetonitrile is added 290 mg (0.99 mmol) of2-(3-chloro-pyridin-2-yl)-5-triluoromethyl-2H-pyrazole-3-carboxylic acidfollowed by 360 μL (4.5 mmol) of pyridine. The mixture is stirred atambient temperature during 30 minutes. Then the suspension is cooled to0° C. and 270 μL (3.5 mmol) of methanesulfonyl chloride is addeddropwise. The resulting mixture is stirred at ambient temperature for 16hours. Then the solvent is evaporated and the residue is triturated witha minimum of cold water. The precipitate, which is formed is filtratedand washed with cold water. The pale yellowish product obtained (426 mg)is engaged in the next step; LC/MS:457/459 (M+H)⁺.

e) Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-5-cyano-1H-indazole-7-carboxylicacid isopropylamide

To a mixture of 426 mg of the above7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazol-3-yl]-5-ethynyl-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-onein 7 mL of 4:1 (v/v) mixture of acetonitrile/water is added 0.79 mL (9.3mmol) of isopropylamine. The reaction mixture is stirred during 4 hoursat ambient temperature and then concentrated in vacuo. Afterpurification by flash chromatography (SiO₂, hexane/ethyl acetate 4:1),250 mg (38%) of product are obtained as a yellow solid; LC/MS:516/518(M+H)⁺; m.p.: 226-229° C.

Example 35 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-5-ethynyl-1H-indazole-7-carboxylicacid bicyclopropyl-1-ylamide

To a solution of 530 mg of the above7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazol-3-yl]-5-ethynyl-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-onein 10 mL of N,N-dimethylformamide, is added 465 mg (3.48 mmol) ofbicyclopropyl-1-ylamine hydrochloride and 485 μL (3.48 mmol) oftriethylamine. The reaction is stirred at 50° C. for 16 hours and thenconcentrated in vacuo. Purification of the residue by flashchromatography (SiO₂, hexane/ethyl acetate 3:7) affords 200 mg (31% overtwo steps) of the product as white solid; LC/MS:554/556 (M+H)⁺, m.p.:246-248° C.

Example 36 Preparation of5-chloro-6-{[5-chloro-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid isopropylamide a) Preparation of5-chloro-7-[5-chloro-2-(3-chloro-pyridin-2-yl)-2H-pyrazol-3-yl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-one

To a suspension of 1.00 g (4.58 mmol) of6-amino-5-chloro-1H-indazole-7-carboxylic acid in 40 mL of anhydrousacetonitrile is added 1.18 g (4.58 mmol) of5-chloro-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acidfollowed by 1.7 mL (20.6 mmol) of pyridine. The mixture is stirred atambient temperature during 30 minutes. Then the suspension is cooled to0° C. and 1.25 mL (16.0 mmol) of methanesulfonyl chloride is addeddropwise. The mixture is stirred at ambient temperature for 6 hours.Then the solvent is evaporated and the residue is triturated with aminimum of cold water. The precipitate, which is formed is filtrated,washed with cold water and dried. Purification by flash chromatography(SiO₂, toluene/methylene chloride/ethyl acetate 10:10:3) affords 910 mg(39%) of the product as a yellowish solid; LC/MS:433/435 (M+H)⁺.

b) Preparation of5-chloro-6-{[5-chloro-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid isopropylamide

To a suspension of 210 mg (0.40 mmol) of the above5-chloro-7-[5-chloro-2-(3-chloro-pyridin-2-yl)-2H-pyrazol-3-yl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-onein 4.2 mL of tetrahydrofuran is added 110 μl (1.3 mmol) ofisopropylamine. The reaction mixture is stirred for 4 hours at ambienttemperature and then concentrated in vacuo. The residue is Purificationof the residue by reverse-phase chromatography affords 111 mg (52%) ofthe product as a white solid; LC/MS:514/516 (M+Na)⁺.

Example 37 Preparation of5-chloro-6-{[5-chloro-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid bicyclopropyl-1-ylamide

To a solution of 400 mg (0.78 mmol) of the above5-chloro-7-[5-chloro-2-(3-chloro-pyridin-2-yl)-2H-pyrazol-3-yl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-onein 8 mL of N,N-dimethylformamide is added 262 mg (1.96 mmol) ofbicyclopropyl-1-ylamine hydrochloride and 273 μL (1.96 mmol) oftriethylamine. The reaction is stirred at 50° C. for 16 hours and thenconcentrated in vacuo. The residue is taken-up with water andtert-butylmethylether. The phases are separated and the aqueous layer iswashed twice with tert-butylmethylether. The combined organic layers arewashed with brine, dried over MgSO₄ and concentrated in vacuo.Purification of the residue by flash chromatography (SiO₂, hexanes/ethylacetate 1:1 to 1:2, gradient) affords 380 mg (91%) of the product as awhite solid; LC/MS:530/532 (M+H)⁺, m.p.: 173-175° C.

Example 38 Preparation of5-chloro-6-{[2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid (3-methyl-1,1-dioxo-1lambda*6*-thietan-3-yl)-amide a) Preparationof5-chloro-7-[2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazol-3-yl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-one

To a suspension of 400 mg (1.89 mmol) of6-amino-5-chloro-1H-indazole-7-carboxylic acid in 16 mL of anhydroustetrahydrofuran is added 479 mg (1.89 mmol) of2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazole-3-carboxylic acidfollowed by 684 μL (8.50 mmol) of pyridine. The mixture is stirred atambient temperature during 30 minutes. Then the suspension is cooled to0° C. and 516 μL (6.66 mmol) of methanesulfonyl chloride are addeddropwise. The mixture is stirred at ambient temperature for 5 hours.Then the solvent is evaporated and the residue is triturated with aminimum of cold water. The precipitate, which is formed is filtrated andwashed with cold water. The pale yellowish product obtained (870 mg) isengaged in the next step; LC/MS:530/532 (M+H)⁺.

b) Preparation of5-chloro-6-{[2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid (3-methyl-thietan-3-yl)-amide

To a solution of 500 mg (1.16 mmol) of the above5-chloro-7-[2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazol-3-yl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-onein 10 mL of N,N-dimethylformamide is added 396 mg (3.49 mmol) of3-methyl-thietan-3-ylamine. The reaction is stirred at 60° C. for 72hours and then concentrated in vacuo. The residue is taken-up with waterand ethyl acetate. The phases are separated and the aqueous layer iswashed three times with ethyl acetate. The combined organic layers arewashed with brine, dried over MgSO₄ and concentrated in vacuo.Purification of the residue by flash chromatography (SiO₂, hexanes/ethylacetate 1:2) affords 276 mg (44%) of the product as a white solid;LC/MS:532/534 (M+H)⁺, m.p.: 162-165° C.

c) Preparation of5-chloro-6-{[2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid (3-methyl-1,1-dioxo-1lambda*6*-thietan-3-yl)-amide

To a mixture of 240 mg (0.41 mmol) of5-chloro-6-{[2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid (3-methyl-thietan-3-yl)-amide in 16.8 mL of methylene chloride atambient temperature is added dropwise 300 mg (1.22 mmol) ofm-chloroperbenzoic acid dissolved in 2.0 mL of methylene chloride. Themixture is stirred at ambient temperature for 16 hours. The solvent isthen evaporated and ethyl acetate and aqueous saturated sodiumbicarbonate are added. The phases are separated and the aqueous layer iswashed with ethyl acetate. The combined organic layers are washed withbrine, dried over MgSO₄ and concentrated in vacuo. Purification of theresidue by flash chromatography (SiO₂, ethyl acetate) affords 115 mg(50%) of the product as a white solid; LC/MS:564/566 (M+H)⁺; m.p.:167-170° C.

Example 39 Preparation of3-bromo-5-chloro-6-{[2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid isopropylamide a) Preparation of6-amino-3-bromo-5-chloro-1H-indazole-7-carboxylic acid methyl ester

To a solution of 9 g (29.92 mmol) of6-amino-5-chloro-1H-indazole-7-carboxylic acid methyl ester in 68 mL ofacetic acid at 80° C., is added dropwise 2 mL (38.89 mmol) of bromine.The mixture is stirred over the night at 80° C. The solvents areevaporated and water is added to the residue. The product isprecipitated at pH 5 by addition of 1N aqueous NaOH, filtrated, washedwith a minimum of water and dried under high vacuum. 1 g (3.28 mmol,11%) of pure product is obtained; LC/MS:305/306 (M+H)⁺.

b) Preparation of 6-amino-3-bromo-5-chloro-1H-indazole-7-carboxylic acid

See step b example 1 for the preparation of this compound with6-amino-3-bromo-5-chloro-1H-indazole-7-carboxylic acid methyl ester asstarting material. After 24 h of reaction time at ambient temperature,the solvents are evaporated and water is added to the residue. Theproduct is precipitated at pH 4 by addition of concentrated HCl,filtrated, washed with a minimum of water and dried on high vacuum pump.The crude solid (832 mg) obtained is used directly in the next step;LC/MS:291/292 (M+H)⁺.

c) Preparation of3-bromo-5-chloro-7-[2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazol-3-yl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-one

To a suspension of 400 mg (1.38 mmol) of6-amino-3-bromo-5-chloro-1H-indazole-7-carboxylic acid in 16 mL ofanhydrous tetrahydrofuran at 10° C., is added 349 mg (1.38 mmol) of2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazole-3-carboxylic acidfollowed by 499 μL (6.20 mmol) of pyridine. Then the suspension iscooled to 0° C. and 376 μL (4.82 mmol) of methanesulfonyl chloride areadded dropwise. The mixture is stirred at ambient temperature over thenight. The reaction is not complete and therefore 166 μL (2.07 mmol) ofpyridine are added followed by 349 mg (1.38 mmol) of2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazole-3-carboxylic acid. Thereaction is stirred again at ambient temperature for 5 hours. Then thesolvent is evaporated and the residue is triturated with a minimum ofcold water. The precipitate, which is formed is filtrated and washedwith cold water. The pale yellowish product obtained is purified byflash chromatography (SiO₂, heptane/ethyl acetate 1:1) affords 200 mg(0.47 mmol, 34%) of the product as a solid; LC/MS:509/511 (M+H)⁺.

d) Preparation of3-bromo-5-chloro-6-{[2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid isopropylamide

To a suspension of 120 mg (0.24 mmol) of the above3-bromo-5-chloro-7-[2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazol-3-yl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-onein 2.4 mL of a mixture acetonitrile:H₂O 4:2 (v/v) is added 60 μL (0.71mmol) of isopropylamine. The reaction mixture is stirred for 6 hours atambient temperature. Brine is then added to the mixture and the productis extracted with ethyl acetate (3 times). The regrouped organic phasesare dried on Na₂SO₄, filtrated and evaporated. The purification of theresidue by flash chromatography (SiO₂, heptane/ethyl acetate 1:2)affords 56 mg (42%) of a white solid; LC/MS:568/570 (M+H)⁺, m.p.:217-218° C.

Example 40 Preparation of3-bromo-5-chloro-6-{[2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazole-3-carbonyl]-amino}-1H-indazole-7-carboxylicacid bicyclopropyl-1-ylamide

To a solution of 120 mg (0.24 mmol) of the above3-bromo-5-chloro-7-[2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazol-3-yl]-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-onein 2.4 mL of N,N-dimethylformamide is added 95 mg (0.71 mmol) ofbicyclopropyl-1-ylamine hydrochloride and 99 μL (0.71 mmol) oftriethylamine. The reaction is stirred at 50° C. for 24 hours and thenconcentrated in vacuo. The residue is taken-up with acetone and afterfiltration the filtrate is evaporated. Purification of the residue byflash chromatography (SiO₂, hexanes/ethyl acetate 1:1) affords 80 mg(56%) of a solid; LC/MS:606/608 (M+H)⁺, m.p.: 190-194° C.

Example 41 Preparation of5-chloro-6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-3-methyl-1H-indazole-7-carboxylicacid isopropylamide a) Preparation of6-amino-5-chloro-3-methyl-1H-indazole-7-carboxylic acid methyl ester

To a solution of 899 mg (5.91 mmol) of9-methoxy-9-bora-bicyclo[3.3.1]nonane in 5 mL of anhydroustetrahydrofuran is added dropwise 3.71 mL (5.91 mmol) of a solution 1Nof methyl lithium in diethylether. After few minutes of stirring, amixture of 6-amino-3-bromo-5-chloro-1H-indazole-7-carboxylic acid methylester, prepared as in step a in example 39, and 104 mg (0.15 mmol) ofbis(triphenylphosphine) palladiumI(II) dichloride in 10 mL of anhydroustetrahydrofuran is added. The reaction mixture is stirred in a microwaveoven at 150° C. for 15 minutes. After filtration over Celite andconcentration in vacuo, the residue is purified by flash chromatography(SiO₂, hexanes/ethyl acetate 1:1) to afford 470 mg of product (66%) as apale yellowish solid; LC/MS:240/242 (M+H)⁺.

b) Preparation of 6-amino-5-chloro-3-methyl-1H-indazole-7-carboxylicacid

See step b example 1 for the preparation of this compound with6-amino-5-chloro-3-methyl-1H-indazole-7-carboxylic acid methyl ester asstarting material. After 24 h of reaction time at ambient temperature,the solvents are evaporated and water is added to the residue. Theproduct is precipitated at pH 4 by addition of concentrated HCl,filtrated, washed with a minimum of water and dried on high vacuum pump.The crude solid (92%) obtained is used directly in the next step;LC/MS:226/228 (M+H)⁺.

c) Preparation of5-chloro-7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazol-3-yl]-3-methyl-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-one

To a suspension of 540 mg (2.39 mmol) of6-amino-5-chloro-3-methyl-1H-indazole-7-carboxylic acid in 22 mL ofanhydrous tetrahydrofuran at 10° C., is added 698 mg (2.39 mmol) of2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carboxylicacid followed by 963 μL (11.97 mmol) of pyridine. Then the suspension iscooled to 0° C. and 748 μL (9.57 mmol) of methanesulfonyl chloride areadded dropwise. The mixture is stirred at ambient temperature for 48hours. Then the solvent is evaporated and the residue is taken-up withacetone. After filtration, the filtrate is evaporated in vacuo. Theresidue obtained is purified by flash chromatography (SiO₂,heptane/ethyl acetate 1:2) and affords 810 mg (1.68 mmol, 70%) of theproduct as a solid; LC/MS:481/483 (M+H)⁺.

d) Preparation of5-chloro-6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-3-methyl-1H-indazole-7-carboxylicacid isopropylamide

To a suspension of 148 mg (0.20 mmol) of the above5-chloro-7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazol-3-yl]-3-methyl-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-onein 5.92 mL of a mixture acetonitrile: H₂O 4:1 (v/v) is added 51 μL (0.60mmol) of isopropylamine. The reaction mixture is stirred for 6 hours atambient temperature. Brine is then added to the mixture and the productis extracted with ethyl acetate (3 times). The regrouped organic phasesare dried on Na₂SO₄, filtrated and evaporated. The purification of theresidue by flash chromatography (SiO₂, heptane/ethyl acetate 1:1)affords 30 mg (28%) of a white solid; LC/MS:540/542 (M+H)⁺, m.p.:235-236° C.

Example 42 Preparation of5-chloro-6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-3-methyl-1H-indazole-7-carboxylicacid bicyclopropyl-1-ylamide

To a solution of 150 mg (0.25 mmol) of the above5-chloro-7-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazol-3-yl]-3-methyl-1H-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalen-9-onein 3 mL of N,N-dimethylformamide is added 100 mg (0.75 mmol) ofbicyclopropyl-1-ylamine hydrochloride and 104 μL (0.75 mmol) oftriethylamine. The reaction is stirred at 50° C. for 24 hours and thenconcentrated in vacuo. The residue is taken-up with acetone and afterfiltration the filtrate is evaporated. Purification of the residue byflash chromatography (SiO₂, hexanes/ethyl acetate 3:2) affords 70 mg(48%) of a solid; LC/MS:578/580 (M+H)⁺, m.p.: 228-229° C.

Example 43 Preparation of6-chloro-7-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-quinoline-8-carboxylicacid isopropylamide a) Preparation of 7-amino-quinoline-8-carboxylicacid

This compound is prepared as described in Chem. Pharm. Bull. 1985, 33,4, 1360 and J. Med. Chem., 2002, 45, 3692; LC/MS:189/190 (M+H)⁺. Thestarting material 7-nitro-quinoline is prepared as in U.S. Pat. No.5,283,336 (1994) and WO03068749.

b) Preparation of2-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazol-3-yl]-3-oxa-1,5-diaza-phenanthren-4-one

To a suspension of 500 mg (2.66 mmol) of 7-amino-quinoline-8-carboxylicacid in 20 mL of anhydrous tetrahydrofuran at 10° C., is added 775 mg(2.66 mmol) of2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carboxylicacid followed by 1.07 mL (13.28 mmol) of pyridine. Then the suspensionis cooled to 0° C. and 830 μL (10.63 mmol) of methanesulfonyl chlorideare added dropwise. The mixture is stirred at ambient temperature for 48hours. Then the solvent is evaporated and the residue is precipitatedwith a minimum of water. The filtration gave 180 mg of product afterdrying on high vacuum pump. The filtrate is evaporated and the residueobtained is purified by flash chromatography to afford 100 mg more ofproduct as a solid. The overall yield is 24%; LC/MS:444/446 (M+H)⁺.

c) Preparation of7-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-quinoline-8-carboxylicacid isopropylamide

To a suspension of 140 mg (0.28 mmol) of the above2-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazol-3-yl]-3-oxa-1,5-diaza-phenanthren-4-onein 5.60 mL of a mixture acetonitrile: H₂O 4:1 (v/v) is added 73 μL (0.85mmol) of isopropylamine. The reaction mixture is stirred for 6 hours atambient temperature. Brine is then added to the mixture and the productis extracted with ethyl acetate (3 times). The regrouped organic phasesare dried on Na₂SO₄, filtrated and evaporated. The purification of theresidue by flash chromatography (SiO₂, heptane and ethyl acetate aseluants) affords 100 mg (70%) of a white solid; LC/MS: 503/505 (M+H)⁺,m.p.: 225-226° C.

Example 44 Preparation of7-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-quinoline-8-carboxylicacid methylamide

To a suspension of 140 mg (0.28 mmol) of the above2-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazol-3-yl]-3-oxa-1,5-diaza-phenanthren-4-onein 5.60 mL of a mixture acetonitrile: H₂O 4:1 (v/v) is added 74 μL (0.85mmol) of methylamine (solution 40% in water). The reaction mixture isstirred for 6 hours at ambient temperature. Brine is then added to themixture and the product is extracted with ethyl acetate (3 times). Theregrouped organic phases are dried on Na₂SO₄, filtrated and evaporated.The purification of the residue by flash chromatography (SiO₂, heptaneand ethyl acetate as eluants) affords 84 mg (62%) of a white solid;LC/MS:475/477 (M+H)⁺, m.p.: 219-220° C.

Example 45 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-quinoline-5-carboxylicacid isopropylamide a) Preparation of 6-amino-quinoline-5-carboxylicacid amide

This compound is prepared as reported in J. Chem. Soc., 1962, 3645starting from the 6-nitroquinoline. Under these conditions we didn't getthe 6-amino-quinoline-5-carboxylic acid as described, but thecorresponding amide; LC/MS:188/189 (M+H)⁺.

b) Preparation of 6-amino-quinoline-5-carboxylic acid methyl ester

To a solution of 2 g (10.68 mmol) of the above6-amino-quinoline-5-carboxylic acid amide in 10.76 mL of absolutemethanol is added 2.34 mL (42.73 mmol) of concentrated sulphuric acid.The reaction is stirred in a microwave during 13 minutes at 140° C. Thereaction is repeated 6 times with flask opening after each run becauseof gas formation. The mixture is then cooled at 0° C. and water isadded. The pH of the mixture is increased slowly to 6 with addition ofan aqueous 6N NaOH solution. The pH is adjusted to 8 with a saturatedaqueous solution of NaHCO₃. The product is extracted with ethyl acetate(4 times) and the combined organic layers are dried on Na₂SO₄, filtratedand evaporated. After flash chromatography purification with heptane andethyl acetate as eluants, 555 mg (26%) of a yellowish solid areobtained; LC/MS: 203/204 (M+H)⁺.

c) Preparation of 6-amino-quinoline-5-carboxylic acid

To a solution of 540 mg (2.19 mmol) of the above6-amino-quinoline-5-carboxylic acid methyl ester in 10.8 mL of dioxaneand 0.54 mL of methanol is added 5.48 mL (5.48 mmol) of an aqueoussolution of NaOH 1N. The reaction is stirred 24 hours at ambienttemperature. Then the solvents are evaporated in vacuo and the residueis suspended in a minimum of water and precipitated at pH 6 by additionof concentrated HCl. After filtration and washing with a minimum ofwater the solid obtained is dried on high vacuum pump to give 245 mg(60%) of a yellowish solid; LC/MS:189/190 (M+H)⁺.

d) Preparation of2-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazol-3-yl]-3-oxa-1,8-diaza-phenanthren-4-one

To a suspension of 240 mg (1.28 mmol) of 6-amino-quinoline-5-carboxylicacid in 9.60 mL of anhydrous tetrahydrofuran at 10° C., is added 372 mg(1.28 mmol) of2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carboxylicacid followed by 5134 (6.38 mmol) of pyridine. Then the suspension iscooled to 0° C. and 398 μL (5.10 mmol) of methanesulfonyl chloride areadded dropwise. The mixture is stirred at ambient temperature for 48hours. Then the solvent is evaporated and the residue is precipitatedwith a minimum of ethyl acetate and washed with ethyl acetate. Afterfiltration, water is added to the filtrate and the new suspension formedis filtrated again. After drying on high vacuum pump 303 mg (54%) ofsolid are obtained; LC/MS:444/446 (M+H)⁺.

e) Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-quinoline-5-carboxylicacid isopropylamide

To a suspension of 150 mg (0.30 mmol) of the above2-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazol-3-yl]-3-oxa-1,8-diaza-phenanthren-4-onein 6 mL of a mixture acetonitrile: H₂O 4:1 (v/v) is added 78 μL (0.91mmol) of isopropylamine. The reaction mixture is stirred for 6 hours atambient temperature. Brine is then added to the mixture and the productis extracted with ethyl acetate (3 times). The regrouped organic phasesare dried on Na₂SO₄, filtrated and evaporated. The purification of theresidue by flash chromatography (SiO₂, heptane/ethyl acetate 1:1)affords 100 mg (65%) of a white solid; LC/MS:503/505 (M+H)⁺, m.p.:182-183° C.

Example 46 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-quinoline-5-carboxylicacid methylamide

To a suspension of 150 mg (0.30 mmol) of the above2-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazol-3-yl]-3-oxa-1,8-diaza-phenanthren-4-onein 6 mL of a mixture acetonitrile: H₂O 4:1 (v/v) is added 79 μL (0.91mmol) of methylamine (solution 40% in water). The reaction mixture isstirred for 6 hours at ambient temperature. Brine is then added to themixture and the product is extracted with ethyl acetate (3 times). Theregrouped organic phases are dried on Na₂SO₄, filtrated and evaporated.The purification of the residue by flash chromatography (SiO₂,heptane/ethyl acetate 1:1) affords 110 mg (76%) of a white solid;LC/MS:475/477 (M+H)⁺, m.p.: 210-211° C.

Example 47 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-7-methyl-quinoline-5-carboxylicacid methylamide a) Preparation of6-amino-7-bromo-quinoline-5-carboxylic acid methyl ester

To a mixture of 6.6 g (32.6 mmol) of 6-amino-quinoline-5-carboxylic acidmethyl ester, prepared as in step b in example 45, in 50 mL ofN,N-dimethylformamide is added 5.80 g (17.78 mmol) ofN-bromosuccinimide. The reaction is stirred at ambient temperature for 4hours. The solvent is then evaporated and the residue is submitted tocolumn chromatography purification on silica gel with ethyl acetate aseluent to afford 1.59 g (17%) of the product as a yellow solid;LC/MS:281/283 (M+H)⁺.

b) Preparation of 6-amino-7-methyl-quinoline-5-carboxylic acid methylester

To 1.59 g (5.66 mmol) of 6-amino-7-bromo-quinoline-5-carboxylic acidmethyl ester in 30 mL of dioxane under an atmosphere of argon is added2.35 g (17.0 mmol) of K₂CO₃, 323 mg (0.28 mmol) oftetrakis(triphenylphsophine)palladium and 710 mg (5.66 mmol) oftrimethylboroxine. The reaction mixture is stirred in a microwave ovenat 180° C. for 10 minutes. After filtration over Celite andconcentration in vacuo, the residue is purified by flash chromatography(SiO₂, ethyl acetate) y to afford 550 mg of product (45%) as a yellowishsolid; LC/MS:217/218 (M+H)⁺.

c) Preparation of 6-amino-7-methyl-quinoline-5-carboxylic acid

To a solution of 550 mg (2.54 mmol) of6-amino-7-methyl-quinoline-5-carboxylic acid methyl ester in 11 mL ofdioxane and 0.5 mL of methanol, is added 6.4 mL (6.4 mmol) of an aqueoussolution of NaOH 1N. The mixture is stirred at ambient temperature for16 hours. The solvents are evaporated and water is added to the residue.The product is precipitated at pH 6 by addition of concentrated HCl,filtrated, washed with a minimum of water and dried on high vacuum pump.The yellow crude solid (282 mg) obtained is used directly in the nextstep; LC/MS: 203/204 (M+H)⁺.

d) Preparation of2-[2-(3-chloro-pyridin-2-yl)-5-hydroxy-2H-pyrazol-3-yl]-10-methyl-3-oxa-1,8-diaza-phenanthren-4-one

To a suspension of 282 mg (1.39 mmol) of6-amino-7-methyl-quinoline-5-carboxylic acid in 11 mL of anhydrous THFis added 407 mg (1.39 mmol) of2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carboxylicacid followed by 560 μL (7.0 mmol) of pyridine. The mixture is stirredat ambient temperature during 30 minutes. Then the suspension is cooledto 0° C. and 430 μL (5.5 mmol) of methanesulfonyl chloride are addeddropwise. The mixture is stirred at ambient temperature for 48 hours.Then the solvent is evaporated and the residue is sequentiallytriturated and filtrated with ethyl acetate and with a minimum of coldwater. Purification of the residue by flash chromatography (SiO₂,heptane/ethyl acetate 1:2) affords 286 mg (45%) of the product as ayellowish solid; LC/MS:468/460 (M+H)⁺.

e) Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-7-methyl-quinoline-5-carboxylicacid methylamide

To a suspension of 143 mg (0.31 mmol) of the above2-[2-(3-chloro-pyridin-2-yl)-5-hydroxy-2H-pyrazol-3-yl]-10-methyl-3-oxa-1,8-diaza-phenanthren-4-onein 5 mL of acetonitrile/water (4:1, v/v), is added 80 μL (0.9 mmol) of40% aqueous methylamine. The reaction mixture is stirred for 6 hours atambient temperature and then concentrated in vacuo. The residue istaken-up with brine and ethyl acetate. The phases are separated and theaqueous layer is washed twice with ethyl acetate. The combined organiclayers are washed with brine, dried over MgSO₄ and concentrated invacuo. Purification of the residue by flash chromatography (SiO₂, ethylacetate) affords 25 mg (16%) of the product as a yellowish solid; LC/MS:489/491 (M+H)⁺, m.p.: 150-152° C. (decomposition).

Example 48 Preparation of6-{[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl]-amino}-7-methyl-quinoline-5-carboxylicacid isopropylamide

To a suspension of 143 mg (0.31 mmol) of the above2-[2-(3-chloro-pyridin-2-yl)-5-hydroxy-2H-pyrazol-3-yl]-10-methyl-3-oxa-1,8-diaza-phenanthren-4-onein 5 mL of acetonitrile/water (4:1, v/v), is added 80 μL (0.9 mmol) ofisopropyalamine. The reaction mixture is stirred for 6 hours at ambienttemperature and then concentrated in vacuo. The residue is taken-up withbrine and ethyl acetate. The phases are separated and the aqueous layeris washed twice with ethyl acetate. The combined organic layers arewashed with brine, dried over MgSO₄ and concentrated in vacuo.Purification of the residue by flash chromatography (SiO₂, ethylacetate) affords 56 mg (35%) of the product as a yellowish solid; LC/MS:517/519 (M+H)⁺, m.p.: 162-168° C. (decomposition).

Example 49 Preparation of 6-amino-5-iodo-1H-indazole-7-carboxylic acidmethyl ester

To a solution of 500 mg (2.61 mmol) of 6-amino-1H-indazole-7-carboxylicacid methyl ester, prepared as in step a in example 10, in 5 mL ofacetonitrile is added 1.29 g (5.73 mmol) of N-iodosuccinimide. Thereaction mixture is stirred at ambient temperature for 1 hour and at 50°C. for 6 hours. The solvent is then evaporated and the residue issuspended in water. Filtration affords 750 mg (91%) of the product as abrown solid; LC/MS:318/319 (M+H)⁺.

TABLE P Physical data of compounds of formula I: Compound Melting No.Structures Point MS/NMR P.1

240-242° C. LC/MS: 513/515 (M + Na)⁺ P.2

239-241° C. LC/MS: 525/527 (M + Na)⁺ P.3

203-205° C. LC/MS: 492/494 (M + H)⁺ P.4

240-242° C. LC/MS: 504/506 (M + H)⁺ P.5

224-227° C. LC/MS: 530/532 (M + H)⁺ P.6

190-192° C. LC/MS: 464/466 (M + H)⁺ P.7

100-105° C. LC/MS: 552/554 (M + H)⁺ P.8

— LC/MS: 568/570 (M + H)⁺ P.9

— LC/MS: 584/586 (M + H)⁺ P.10

245-247° C. LC/MS: 526/528 (M + H)⁺ P.11

>250° C. LC/MS: 538/540 (M + H)⁺ P.12

>250° C. LC/MS: 564/566 (M + H)⁺ P.13

100-105° C. LC/MS: 586/588 (M + H)⁺ P.14

— LC/MS: 602/604 (M + H)⁺; 624/626 (M + Na)⁺ P.15

173-176° C. LC/MS: 640/642 (M + Na)⁺ P.16

189-190° C. LC/MS: 570/572 (M + H)⁺ P.17

>255° C. LC/MS: 564/566 (M + Na)⁺ P.18

212-214° C. LC/MS: 608/610 (M + H)⁺ P.19

144-150° C. LC/MS: 582/584 (M + H)⁺ P.20

>240° C. LC/MS: 531/533 (M + H)⁺ P.21

>230° C. LC/MS: 547/549 (M + H)⁺ P.22

>134° C. — P.23

>230° C. LC/MS: 517/519 (M + H)⁺ P.24

213-220° C. LC/MS: 587/589 (M + H)⁺ P.25

— LC/MS: 519/520 (M + H)⁺ P.26

— LC/MS: 555/557 (M + H)⁺ P.27

148-151° C. LC/MS: 468/470 (M + H)⁺ P.28

150-154° C. LC/MS: 506/508 (M + H)⁺ P.29

>255° C. LC/MS: 498/500 (M + H)⁺ P.30

243-244° C. LC/MS: 512/514 (M + H)⁺ P.31

148-150° C. LC/MS: 550/552 (M + H)⁺ P.32

159-160° C. decomposition LC/MS: 570/572 (M + H)⁺ P.33

135-140° C. decomposition LC/MS: 632/634 (M + H)⁺ P.34

243-244° C. LC/MS: 664/666 (M + H)⁺ P.35

141-144° C. LC/MS: 554/558 (M + Na)⁺ P.36

144-145° C. decomposition LC/MS: 568/570 (M + Na)⁺ P.37

237-238° C. LC/MS: 524/526 (M + H)⁺ P.38

— LC/MS: 547/549 (M + H)⁺ P.39

— LC/MS: 509/511 (M + H)⁺ P.40

186-187° C. LC/MS: 510/512 (M + Na)⁺ P.41

237-238° C. LC/MS: 578/580 (M + Na)⁺ P.42

217-218° C. LC/MS: 560/562 (M + Na)⁺ P.43

— LC/MS: 516/518 (M + Na)⁺ P.44

— LC/MS: 506/508 (M + H)⁺ P.45

173-175° C. LC/MS: 532/534 (M + H)⁺ P.46

182-184° C. LC/MS: 576/578 (M + H)⁺ P.47

155-157° C. LC/MS: 526/528 (M + H)⁺ P.48

240-241° C. LC/MS: 594/596 (M + H)⁺ P.49

159-162° C. LC/MS: 544/546 (M + H)⁺ P.50

149-152° C. LC/MS: 520/522 (M + H)⁺ P.51

151-154° C. LC/MS: 594/596 (M + H)⁺ P.52

247-250° C. LC/MS: 536/538 (M + H)⁺ P.53

154-156° C. LC/MS: 517/519 (M + H)⁺ P.54

275-277° C. LC/MS: 626/628 (M + H)⁺ P.55

224-227° C. LC/MS: 479/481 (M + H)⁺ P.56

250-253° C. LC/MS: 488/490 (M + H)⁺ P.57

159-161° C. LC/MS: 548/550 (M + H)⁺ P.58

215-216° C. LC/MS: 474/476 (M + H)⁺ P.59

162-165° C. LC/MS: 532/534 (M + H)⁺ P.60

>250° C. LC/MS: 580/582 (M + H)⁺ P.61

167-170° C. LC/MS: 654/566 (M + H)⁺ P.62

224-227° C. LC/MS: 526/528 (M + H)⁺ P.63

217-218° C. LC/MS: 568/570 (M + H)⁺ P.64

190-194° C. LC/MS: 606/608 (M + H)⁺ P.65

163-166° C. LC/MS: 518/520 (M + H)⁺ P.66

226-229° C. LC/MS: 516/518 (M + H)⁺ P.67

248-250° C. LC/MS: 606/608 (M + H)⁺ P.68

228-229° C. LC/MS: 644/646 (M + H)⁺ P.69

235-236° C. LC/MS: 540/542 (M + H)⁺ P.70

240-242° C. LC/MS: 574/576 (M + H)⁺ P.71

170-173° C. LC/MS: 556/558 (M + H)⁺ P.72

228-229° C. LC/MS: 578/580 (M + H)⁺ P.73

225-226° C. LC/MS: 503/505 (M + H)⁺ P.74

219-220° C. LC/MS: 475/477 (M + H)⁺ P.75

182-183° C. LC/MS: 503/505 (M + H)⁺ P.76

210-211° C. LC/MS: 475/477 (M + H)⁺ P.77

m.p.: 150-152° C. decomposition LC/MS: 489/491 (M + H)⁺ P.78

m.p.: 162-168° C. decomposition LC/MS: 517/519 (M + H)⁺ P.79

246-248° C. LC/MS: 554/556 (M + H)⁺ P.80

233-236° C. LC/MS: 498/500 (M + H)⁺ P.81

218-221° C. LC/MS: 536/538 (M + H)⁺

The compounds according to the following tables can be preparedanalogously. The examples which follow are intended to illustrate theinvention and show preferred compounds of formula I.

TABLE A Compounds of formula Ib: (Ib)

Line R₁a R₁₀₀ R₂₀ A.1.1 CH₃ CF₃ H A.1.2 CH₃ CF₃ CH₃ A.1.3 CH₃ CF₃ CH₂CH₃A.1.4 CH₃ CF₃ CH(CH₃)CH₃ A.1.5 CH₃ CF₃ C(CH₃)(CH₃)CH₃ A.1.6 CH₃ CF₃

A.1.7 CH₃ CF₃

A.1.8 CH₃ CF₃

A.1.9 CH₃ CF₃

A.1.10 CH₃ CF₃ CH(CH₃)₂CH₂SCH₃ A.1.11 CH₃ CF₃ CH(CH₃)₂S(O)CH₃ A.1.12 CH₃CF₃ CH(CH₃)₂S(O)₂CH₃ A.1.13 CH₃ OCH₂CF₃ H A.1.14 CH₃ OCH₂CF₃ CH₃ A.1.15CH₃ OCH₂CF₃ CH₂CH₃ A.1.16 CH₃ OCH₂CF₃ CH(CH₃)CH₃ A.1.17 CH₃ OCH₂CF₃C(CH₃)(CH₃)CH₃ A.1.18 CH₃ OCH₂CF₃

A.1.19 CH₃ OCH₂CF₃

A.1.20 CH₃ OCH₂CF₃

A.1.21 CH₃ OCH₂CF₃

A.1.22 CH₃ OCH₂CF₃ CH(CH₃)₂CH₂SCH₃ A.1.23 CH₃ OCH₂CF₃ CH(CH₃)₂CH₂S(O)CH₃A.1.24 CH₃ OCH₂CF₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.25 CH₃ Br H A.1.26 CH₃ Br CH₃A.1.27 CH₃ Br CH₂CH₃ A.1.28 CH₃ Br CH(CH₃)CH₃ A.1.29 CH₃ BrC(CH₃)(CH₃)CH₃ A.1.30 CH₃ Br

A.1.31 CH₃ Br

A.1.32 CH₃ Br

A.1.33 CH₃ Br

A.1.34 CH₃ Br CH(CH₃)₂CH₂SCH₃ A.1.35 CH₃ Br CH(CH₃)₂CH₂S(O)CH₃ A.1.36CH₃ Br CH(CH₃)₂CH₂S(O)₂CH₃ A.1.37 CH₃ Cl H A.1.38 CH₃ Cl CH₃ A.1.39 CH₃Cl CH₂CH₃ A.1.40 CH₃ Cl CH(CH₃)CH₃ A.1.41 CH₃ Cl C(CH₃)(CH₃)CH₃ A.1.42CH₃ Cl

A.1.43 CH₃ Cl

A.1.44 CH₃ Cl

A.1.45 CH₃ Cl

A.1.46 CH₃ Cl CH(CH₃)₂CH₂SCH₃ A.1.47 CH₃ Cl CH(CH₃)₂CH₂S(O)CH₃ A.1.48CH₃ Cl CH(CH₃)₂CH₂S(O)₂CH₃ A.1.49 CH₃ CF₂H H A.1.50 CH₃ CF₂H CH₃ A.1.51CH₃ CF₂H CH₂CH₃ A.1.52 CH₃ CF₂H CH(CH₃)CH₃ A.1.53 CH₃ CF₂HC(CH₃)(CH₃)CH₃ A.1.54 CH₃ CF₂H

A.1.55 CH₃ CF₂H

A.1.56 CH₃ CF₂H

A.1.57 CH₃ CF₂H

A.1.58 CH₃ CF₂H CH(CH₃)₂CH₂SCH₃ A.1.59 CH₃ CF₂H CH(CH₃)₂CH₂S(O)CH₃A.1.60 CH₃ CF₂H CH(CH₃)₂CH₂S(O)₂CH₃ A.1.61 CH₃ OCF₃ H A.1.62 CH₃ OCF₃CH₃ A.1.63 CH₃ OCF₃ CH₂CH₃ A.1.64 CH₃ OCF₃ CH(CH₃)CH₃ A.1.65 CH₃ OCF₃C(CH₃)(CH₃)CH₃ A.1.66 CH₃ OCF₃

A.1.67 CH₃ OCF₃

A.1.68 CH₃ OCF₃

A.1.69 CH₃ OCF₃

A.1.70 CH₃ OCF₃ CH(CH₃)₂CH₂SCH₃ A.1.71 CH₃ OCF₃ CH(CH₃)₂CH₂S(O)CH₃A.1.72 CH₃ OCF₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.73 Cl CF₃ H A.1.74 Cl CF₃ CH₃A.1.75 Cl CF₃ CH₂CH₃ A.1.76 Cl CF₃ CH(CH₃)CH₃ A.1.77 Cl CF₃C(CH₃)(CH₃)CH₃ A.1.78 Cl CF₃

A.1.79 Cl CF₃

A.1.80 Cl CF₃

A.1.81 Cl CF₃

A.1.82 Cl CF₃ CH(CH₃)₂CH₂SCH₃ A.1.83 Cl CF₃ CH(CH₃)₂CH₂S(O)CH₃ A.1.84 ClCF₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.85 Cl OCH₂CF₃ H A.1.86 Cl OCH₂CF₃ CH₃ A.1.87Cl OCH₂CF₃ CH₂CH₃ A.1.88 Cl OCH₂CF₃ CH(CH₃)CH₃ A.1.89 Cl OCH₂CF₃C(CH₃)(CH₃)CH₃ A.1.90 Cl OCH₂CF₃

A.1.91 Cl OCH₂CF₃

A.1.92 Cl OCH₂CF₃

A.1.93 Cl OCH₂CF₃

A.1.94 Cl OCH₂CF₃ CH(CH₃)₂CH₂SCH₃ A.1.95 Cl OCH₂CF₃ CH(CH₃)₂CH₂S(O)CH₃A.1.96 Cl OCH₂CF₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.97 Cl Br H A.1.98 Cl Br CH₃A.1.99 Cl Br CH₂CH₃ A.1.100 Cl Br CH(CH₃)CH₃ A.1.101 Cl BrC(CH₃)(CH₃)CH₃ A.1.102 Cl Br

A.1.103 Cl Br

A.1.104 Cl Br

A.1.105 Cl Br

A.1.106 Cl Br CH(CH₃)₂CH₂SCH₃ A.1.107 Cl Br CH(CH₃)₂CH₂S(O)CH₃ A.1.108Cl Br CH(CH₃)₂CH₂S(O)₂CH₃ A.1.109 Cl Cl H A.1.110 Cl Cl CH₃ A.1.111 ClCl CH₂CH₃ A.1.112 Cl Cl CH(CH₃)CH₃ A.1.113 Cl Cl C(CH₃)(CH₃)CH₃ A.1.114Cl Cl

A.1.115 Cl Cl

A.1.116 Cl Cl

A.1.117 Cl Cl

A.1.118 Cl Cl CH(CH₃)₂CH₂SCH₃ A.1.119 Cl Cl CH(CH₃)₂CH₂S(O)CH₃ A.1.120Cl Cl CH(CH₃)₂CH₂S(O)₂CH₃ A.1.121 Cl CF₂H H A.1.122 Cl CF₂H CH₃ A.1.123Cl CF₂H CH₂CH₃ A.1.124 Cl CF₂H CH(CH₃)CH₃ A.1.125 Cl CF₂H C(CH₃)(CH₃)CH₃A.1.126 Cl CF₂H

A.1.127 Cl CF₂H

A.1.128 Cl CF₂H

A.1.129 Cl CF₂H

A.1.130 Cl CF₂H CH(CH₃)₂CH₂SCH₃ A.1.131 Cl CF₂H CH(CH₃)₂CH₂S(O)CH₃A.1.132 Cl CF₂H CH(CH₃)₂CH₂S(O)₂CH₃ A.1.133 Cl OCF₃ H A.1.134 Cl OCF₃CH₃ A.1.135 Cl OCF₃ CH₂CH₃ A.1.136 Cl OCF₃ CH(CH₃)CH₃ A.1.137 Cl OCF₃C(CH₃)(CH₃)CH₃ A.1.138 Cl OCF₃

A.1.139 Cl OCF₃

A.1.140 Cl OCF₃

A.1.141 Cl OCF₃

A.1.142 Cl OCF₃ CH(CH₃)₂CH₂SCH₃ A.1.143 Cl OCF₃ CH(CH₃)₂CH₂S(O)CH₃A.1.144 Cl OCF₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.145 Br CF₃ H A.1.146 Br CF₃ CH₃A.1.147 Br CF₃ CH₂CH₃ A.1.148 Br CF₃ CH(CH₃)CH₃ A.1.149 Br CF₃C(CH₃)(CH₃)CH₃ A.1.150 Br CF₃

A.1.151 Br CF₃

A.1.152 Br CF₃

A.1.153 Br CF₃

A.1.154 Br CF₃ CH(CH₃)₂CH₂SCH₃ A.1.155 Br CF₃ CH(CH₃)₂CH₂S(O)CH₃ A.1.156Br CF₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.157 Br OCH₂CF₃ H A.1.158 Br OCH₂CF₃ CH₃A.1.159 Br OCH₂CF₃ CH₂CH₃ A.1.160 Br OCH₂CF₃ CH(CH₃)CH₃ A.1.161 BrOCH₂CF₃ C(CH₃)(CH₃)CH₃ A.1.162 Br OCH₂CF₃

A.1.163 Br OCH₂CF₃

A.1.164 Br OCH₂CF₃

A.1.165 Br OCH₂CF₃

A.1.166 Br OCH₂CF₃ CH(CH₃)₂CH₂SCH₃ A.1.167 Br OCH₂CF₃ CH(CH₃)₂CH₂S(O)CH₃A.1.168 Br OCH₂CF₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.169 Br Br H A.1.170 Br Br CH₃A.1.171 Br Br CH₂CH₃ A.1.172 Br Br CH(CH₃)CH₃ A.1.173 Br BrC(CH₃)(CH₃)CH₃ A.1.174 Br Br

A.1.175 Br Br

A.1.176 Br Br

A.1.177 Br Br

A.1.178 Br Br CH(CH₃)₂CH₂SCH₃ A.1.179 Br Br CH(CH₃)₂CH₂S(O)CH₃ A.1.180Br Br CH(CH₃)₂CH₂S(O)₂CH₃ A.1.181 Br Cl H A.1.182 Br Cl CH₃ A.1.183 BrCl CH₂CH₃ A.1.184 Br Cl CH(CH₃)CH₃ A.1.185 Br Cl C(CH₃)(CH₃)CH₃ A.1.186Br Cl

A.1.187 Br Cl

A.1.188 Br Cl

A.1.189 Br Cl

A.1.190 Br Cl CH(CH₃)₂CH₂SCH₃ A.1.191 Br Cl CH(CH₃)₂CH₂S(O)CH₃ A.1.192Br Cl CH(CH₃)₂CH₂S(O)₂CH₃ A.1.193 Br CF₂H H A.1.194 Br CF₂H CH₃ A.1.195Br CF₂H CH₂CH₃ A.1.196 Br CF₂H CH(CH₃)CH₃ A.1.197 Br CF₂H C(CH₃)(CH₃)CH₃A.1.198 Br CF₂H

A.1.199 Br CF₂H

A.1.200 Br CF₂H

A.1.201 Br CF₂H

A.1.202 Br CF₂H CH(CH₃)₂CH₂SCH₃ A.1.203 Br CF₂H CH(CH₃)₂CH₂S(O)CH₃A.1.204 Br CF₂H CH(CH₃)₂CH₂S(O)₂CH₃ A.1.205 Br OCF₃ H A.1.206 Br OCF₃CH₃ A.1.207 Br OCF₃ CH₂CH₃ A.1.208 Br OCF₃ CH(CH₃)CH₃ A.1.209 Br OCF₃C(CH₃)(CH₃)CH₃ A.1.210 Br OCF₃

A.1.211 Br OCF₃

A.1.212 Br OCF₃

A.1.213 Br OCF₃

A.1.214 Br OCF₃ CH(CH₃)₂CH₂SCH₃ A.1.215 Br OCF₃ CH(CH₃)₂CH₂S(O)CH₃A.1.216 Br OCF₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.217 CN CF₃ H A.1.218 CN CF₃ CH₃A.1.219 CN CF₃ CH₂CH₃ A.1.220 CN CF₃ CH(CH₃)CH₃ A.1.221 CN CF₃C(CH₃)(CH₃)CH₃ A.1.222 CN CF₃

A.1.223 CN CF₃

A.1.224 CN CF₃

A.1.225 CN CF₃

A.1.226 CN CF₃ CH(CH₃)₂CH₂SCH₃ A.1.227 CN CF₃ CH(CH₃)₂CH₂S(O)CH₃ A.1.228CN CF₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.229 CN OCH₂CF₃ H A.1.230 CN OCH₂CF₃ CH₃A.1.231 CN OCH₂CF₃ CH₂CH₃ A.1.232 CN OCH₂CF₃ CH(CH₃)CH₃ A.1.233 CNOCH₂CF₃ C(CH₃)(CH₃)CH₃ A.1.234 CN OCH₂CF₃

A.1.235 CN OCH₂CF₃

A.1.236 CN OCH₂CF₃

A.1.237 CN OCH₂CF₃

A.1.238 CN OCH₂CF₃ CH(CH₃)₂CH₂SCH₃ A.1.239 CN OCH₂CF₃ CH(CH₃)₂CH₂S(O)CH₃A.1.240 CN OCH₂CF₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.241 CN Br H A.1.242 CN Br CH₃A.1.243 CN Br CH₂CH₃ A.1.244 CN Br CH(CH₃)CH₃ A.1.245 CN BrC(CH₃)(CH₃)CH₃ A.1.246 CN Br

A.1.247 CN Br

A.1.248 CN Br

A.1.249 CN Br

A.1.250 CN Br CH(CH₃)₂CH₂SCH₃ A.1.251 CN Br CH(CH₃)₂CH₂S(O)CH₃ A.1.252CN Br CH(CH₃)₂CH₂S(O)₂CH₃ A.1.253 CN Cl H A.1.254 CN Cl CH₃ A.1.255 CNCl CH₂CH₃ A.1.256 CN Cl CH(CH₃)CH₃ A.1.257 CN Cl C(CH₃)(CH₃)CH₃ A.1.258CN Cl

A.1.259 CN Cl

A.1.260 CN Cl

A.1.261 CN Cl

A.1.262 CN Cl CH(CH₃)₂CH₂SCH₃ A.1.263 CN Cl CH(CH₃)₂CH₂S(O)CH₃ A.1.264CN Cl CH(CH₃)₂CH₂S(O)₂CH₃ A.1.265 CN CF₂H H A.1.266 CN CF₂H CH₃ A.1.267CN CF₂H CH₂CH₃ A.1.268 CN CF₂H CH(CH₃)CH₃ A.1.269 CN CF₂H C(CH₃)(CH₃)CH₃A.1.270 CN CF₂H

A.1.271 CN CF₂H

A.1.272 CN CF₂H

A.1.273 CN CF₂H

A.1.274 CN CF₂H CH(CH₃)₂CH₂SCH₃ A.1.275 CN CF₂H CH(CH₃)₂CH₂S(O)CH₃A.1.276 CN CF₂H CH(CH₃)₂CH₂S(O)₂CH₃ A.1.277 CN OCF₃ H A.1.278 CN OCF₃CH₃ A.1.279 CN OCF₃ CH₂CH₃ A.1.280 CN OCF₃ CH(CH₃)CH₃ A.1.281 CN OCF₃C(CH₃)(CH₃)CH₃ A.1.282 CN OCF₃

A.1.283 CN OCF₃

A.1.284 CN OCF₃

A.1.285 CN OCF₃

A.1.286 CN OCF₃ CH(CH₃)₂CH₂SCH₃ A.1.287 CN OCF₃ CH(CH₃)₂CH₂S(O)CH₃A.1.288 CN OCF₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.289 I CF₃ H A.1.290 I CF₃ CH₃A.1.291 I CF₃ CH₂CH₃ A.1.292 I CF₃ CH(CH₃)CH₃ A.1.293 I CF₃C(CH₃)(CH₃)CH₃ A.1.294 I CF₃

A.1.295 I CF₃

A.1.296 I CF₃

A.1.297 I CF₃

A.1.298 I CF₃ CH(CH₃)₂CH₂SCH₃ A.1.299 I CF₃ CH(CH₃)₂CH₂S(O)CH₃ A.1.300 ICF₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.301 I OCH₂CF₃ H A.1.302 I OCH₂CF₃ CH₃A.1.303 I OCH₂CF₃ CH₂CH₃ A.1.304 I OCH₂CF₃ CH(CH₃)CH₃ A.1.305 I OCH₂CF₃C(CH₃)(CH₃)CH₃ A.1.306 I OCH₂CF₃

A.1.307 I OCH₂CF₃

A.1.308 I OCH₂CF₃

A.1.309 I OCH₂CF₃

A.1.310 I OCH₂CF₃ CH(CH₃)₂CH₂SCH₃ A.1.311 I OCH₂CF₃ CH(CH₃)₂CH₂S(O)CH₃A.1.312 I OCH₂CF₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.313 I Br H A.1.314 I Br CH₃A.1.315 I Br CH₂CH₃ A.1.316 I Br CH(CH₃)CH₃ A.1.317 I Br C(CH₃)(CH₃)CH₃A.1.318 I Br

A.1.319 I Br

A.1.320 I Br

A.1.321 I Br

A.1.322 I Br CH(CH₃)₂CH₂SCH₃ A.1.323 I Br CH(CH₃)₂CH₂S(O)CH₃ A.1.324 IBr CH(CH₃)₂CH₂S(O)₂CH₃ A.1.325 I Cl H A.1.326 I Cl CH₃ A.1.327 I ClCH₂CH₃ A.1.328 I Cl CH(CH₃)CH₃ A.1.329 I Cl C(CH₃)(CH₃)CH₃ A.1.330 I Cl

A.1.331 I Cl

A.1.332 I Cl

A.1.333 I Cl

A.1.334 I Cl CH(CH₃)₂CH₂SCH₃ A.1.335 I Cl CH(CH₃)₂CH₂S(O)CH₃ A.1.336 ICl CH(CH₃)₂CH₂S(O)₂CH₃ A.1.337 I CF₂H H A.1.338 I CF₂H CH₃ A.1.339 ICF₂H CH₂CH₃ A.1.340 I CF₂H CH(CH₃)CH₃ A.1.341 I CF₂H C(CH₃)(CH₃)CH₃A.1.342 I CF₂H

A.1.343 I CF₂H

A.1.344 I CF₂H

A.1.345 I CF₂H

A.1.346 I CF₂H CH(CH₃)₂CH₂SCH₃ A.1.347 I CF₂H CH(CH₃)₂CH₂S(O)CH₃ A.1.348I CF₂H CH(CH₃)₂CH₂S(O)₂CH₃ A.1.349 I OCF₃ H A.1.350 I OCF₃ CH₃ A.1.351 IOCF₃ CH₂CH₃ A.1.352 I OCF₃ CH(CH₃)CH₃ A.1.353 I OCF₃ C(CH₃)(CH₃)CH₃A.1.354 I OCF₃

A.1.355 I OCF₃

A.1.356 I OCF₃

A.1.357 I OCF₃

A.1.358 I OCF₃ CH(CH₃)₂CH₂SCH₃ A.1.359 I OCF₃ CH(CH₃)₂CH₂S(O)CH₃ A.1.360I OCF₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.361 C≡CH CF₃ H A.1.362 C≡CH CF₃ CH₃A.1.363 C≡CH CF₃ CH₂CH₃ A.1.364 C≡CH CF₃ CH(CH₃)CH₃ A.1.365 C≡CH CF₃C(CH₃)(CH₃)CH₃ A.1.366 C≡CH CF₃

A.1.367 C≡CH CF₃

A.1.368 C≡CH CF₃

A.1.369 C≡CH CF₃

A.1.370 C≡CH CF₃ CH(CH₃)₂CH₂SCH₃ A.1.371 C≡CH CF₃ CH(CH₃)₂CH₂S(O)CH₃A.1.372 C≡CH CF₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.373 C≡CH OCH₂CF₃ H A.1.374 C≡CHOCH₂CF₃ CH₃ A.1.375 C≡CH OCH₂CF₃ CH₂CH₃ A.1.376 C≡CH OCH₂CF₃ CH(CH₃)CH₃A.1.377 C≡CH OCH₂CF₃ C(CH₃)(CH₃)CH₃ A.1.378 C≡CH OCH₂CF₃

A.1.379 C≡CH OCH₂CF₃

A.1.380 C≡CH OCH₂CF₃

A.1.381 C≡CH OCH₂CF₃

A.1.382 C≡CH OCH₂CF₃ CH(CH₃)₂CH₂SCH₃ A.1.383 C≡CH OCH₂CF₃CH(CH₃)₂CH₂S(O)CH₃ A.1.384 C≡CH OCH₂CF₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.385 C≡CHBr H A.1.386 C≡CH Br CH₃ A.1.387 C≡CH Br CH₂CH₃ A.1.388 C≡CH BrCH(CH₃)CH₃ A.1.389 C≡CH Br C(CH₃)(CH₃)CH₃ A.1.390 C≡CH Br

A.1.391 C≡CH Br

A.1.392 C≡CH Br

A.1.393 C≡CH Br

A.1.394 C≡CH Br CH(CH₃)₂CH₂SCH₃ A.1.395 C≡CH Br CH(CH₃)₂CH₂S(O)CH₃A.1.396 C≡CH Br CH(CH₃)₂CH₂S(O)₂CH₃ A.1.397 C≡CH Cl H A.1.398 C≡CH ClCH₃ A.1.399 C≡CH Cl CH₂CH₃ A.1.400 C≡CH Cl CH(CH₃)CH₃ A.1.401 C≡CH ClC(CH₃)(CH₃)CH₃ A.1.402 C≡CH Cl

A.1.403 C≡CH Cl

A.1.404 C≡CH Cl

A.1.405 C≡CH Cl

A.1.406 C≡CH Cl CH(CH₃)₂CH₂SCH₃ A.1.407 C≡CH Cl CH(CH₃)₂CH₂S(O)CH₃A.1.408 C≡CH Cl CH(CH₃)₂CH₂S(O)₂CH₃ A.1.409 C≡CH CF₂H H A.1.410 C≡CHCF₂H CH₃ A.1.411 C≡CH CF₂H CH₂CH₃ A.1.412 C≡CH CF₂H CH(CH₃)CH₃ A.1.413C≡CH CF₂H C(CH₃)(CH₃)CH₃ A.1.414 C≡CH CF₂H

A.1.415 C≡CH CF₂H

A.1.416 C≡CH CF₂H

A.1.417 C≡CH CF₂H

A.1.418 C≡CH CF₂H CH(CH₃)₂CH₂SCH₃ A.1.419 C≡CH CF₂H CH(CH₃)₂CH₂S(O)CH₃A.1.420 C≡CH CF₂H CH(CH₃)₂CH₂S(O)₂CH₃ A.1.421 C≡CH OCF₃ H A.1.422 C≡CHOCF₃ CH₃ A.1.423 C≡CH OCF₃ CH₂CH₃ A.1.424 C≡CH OCF₃ CH(CH₃)CH₃ A.1.425C≡CH OCF₃ C(CH₃)(CH₃)CH₃ A.1.426 C≡CH OCF₃

A.1.427 C≡CH OCF₃

A.1.428 C≡CH OCF₃

A.1.429 C≡CH OCF₃

A.1.430 C≡CH OCF₃ CH(CH₃)₂CH₂SCH₃ A.1.431 C≡CH OCF₃ CH(CH₃)₂CH₂S(O)CH₃A.1.432 C≡CH OCF₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.433 H CF₃ H A.1.434 H CF₃ CH₃A.1.435 H CF₃ CH₂CH₃ A.1.436 H CF₃ CH(CH₃)CH₃ A.1.437 H CF₃C(CH₃)(CH₃)CH₃ A.1.438 H CF₃

A.1.439 H CF₃

A.1.440 H CF₃

A.1.441 H CF₃

A.1.442 H CF₃ CH(CH₃)₂CH₂SCH₃ A.1.443 H CF₃ CH(CH₃)₂CH₂S(O)CH₃ A.1.444 HCF₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.445 H OCH₂CF₃ H A.1.446 H OCH₂CF₃ CH₃A.1.447 H OCH₂CF₃ CH₂CH₃ A.1.448 H OCH₂CF₃ CH(CH₃)CH₃ A.1.449 H OCH₂CF₃C(CH₃)(CH₃)CH₃ A.1.450 H OCH₂CF₃

A.1.451 H OCH₂CF₃

A.1.452 H OCH₂CF₃

A.1.453 H OCH₂CF₃

A.1.454 H OCH₂CF₃ CH(CH₃)₂CH₂SCH₃ A.1.455 H OCH₂CF₃ CH(CH₃)₂CH₂S(O)CH₃A.1.456 H OCH₂CF₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.457 H Br H A.1.458 H Br CH₃A.1.459 H Br CH₂CH₃ A.1.460 H Br CH(CH₃)CH₃ A.1.461 H Br C(CH₃)(CH₃)CH₃A.1.462 H Br

A.1.463 H Br

A.1.464 H Br

A.1.465 H Br

A.1.466 H Br CH(CH₃)₂CH₂SCH₃ A.1.467 H Br CH(CH₃)₂CH₂S(O)CH₃ A.1.468 HBr CH(CH₃)₂CH₂S(O)₂CH₃ A.1.469 H Cl H A.1.470 H Cl CH₃ A.1.471 H ClCH₂CH₃ A.1.472 H Cl CH(CH₃)CH₃ A.1.473 H Cl C(CH₃)(CH₃)CH₃ A.1.474 H Cl

A.1.475 H Cl

A.1.476 H Cl

A.1.477 H Cl

A.1.478 H Cl CH(CH₃)₂CH₂SCH₃ A.1.479 H Cl CH(CH₃)₂CH₂S(O)CH₃ A.1.480 HCl CH(CH₃)₂CH₂S(O)₂CH₃ A.1.481 H CF₂H H A.1.482 H CF₂H CH₃ A.1.483 HCF₂H CH₂CH₃ A.1.484 H CF₂H CH(CH₃)CH₃ A.1.485 H CF₂H C(CH₃)(CH₃)CH₃A.1.486 H CF₂H

A.1.487 H CF₂H

A.1.488 H CF₂H

A.1.489 H CF₂H

A.1.490 H CF₂H CH(CH₃)₂CH₂SCH₃ A.1.491 H CF₂H CH(CH₃)₂CH₂S(O)CH₃ A.1.492H CF₂H CH(CH₃)₂CH₂S(O)₂CH₃ A.1.493 H OCF₃ H A.1.494 H OCF₃ CH₃ A.1.495 HOCF₃ CH₂CH₃ A.1.496 H OCF₃ CH(CH₃)CH₃ A.1.497 H OCF₃ C(CH₃)(CH₃)CH₃A.1.498 H OCF₃

A.1.499 H OCF₃

A.1.500 H OCF₃

A.1.501 H OCF₃

A.1.502 H OCF₃ CH(CH₃)₂CH₂SCH₃ A.1.503 H OCF₃ CH(CH₃)₂CH₂S(O)CH₃ A.1.504H OCF₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.505 Cl OCH₃ H A.1.506 Cl OCH₃ CH₃ A.1.507Cl OCH₃ CH₂CH₃ A.1.508 Cl OCH₃ CH(CH₃)CH₃ A.1.509 Cl OCH₃ C(CH₃)(CH₃)CH₃A.1.510 Cl OCH₃

A.1.511 Cl OCH₃

A.1.512 Cl OCH₃

A.1.513 Cl

A.1.514 Cl OCH₃ CH(CH₃)₂CH₂SCH₃ A.1.515 Cl OCH₃ CH(CH₃)₂CH₂S(O)CH₃A.1.516 Cl OCH₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.517 Br OCH₃ H A.1.518 Br OCH₃CH₃ A.1.519 Br OCH₃ CH₂CH₃ A.1.520 Br OCH₃ CH(CH₃)CH₃ A.1.521 Br OCH₃C(CH₃)(CH₃)CH₃ A.1.522 Br OCH₃

A.1.523 Br OCH₃

A.1.524 Br OCH₃

A.1.525 Br

A.1.526 Br OCH₃ CH(CH₃)₂CH₂SCH₃ A.1.527 Br OCH₃ CH(CH₃)₂CH₂S(O)CH₃A.1.528 Br OCH₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.529 CH₃ OCH₃ H A.1.530 CH₃ OCH₃CH₃ A.1.531 CH₃ OCH₃ CH₂CH₃ A.1.532 CH₃ OCH₃ CH(CH₃)CH₃ A.1.533 CH₃ OCH₃C(CH₃)(CH₃)CH₃ A.1.534 CH₃ OCH₃

A.1.535 CH₃ OCH₃

A.1.536 CH₃ OCH₃

A.1.537 CH₃

A.1.538 CH₃ OCH₃ CH(CH₃)₂CH₂SCH₃ A.1.539 CH₃ OCH₃ CH(CH₃)₂CH₂S(O)CH₃A.1.540 CH₃ OCH₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.541 H OCH₃ H A.1.542 H OCH₃ CH₃A.1.543 H OCH₃ CH₂CH₃ A.1.544 H OCH₃ CH(CH₃)CH₃ A.1.545 H OCH₃C(CH₃)(CH₃)CH₃ A.1.546 H OCH₃

A.1.547 H OCH₃

A.1.548 H OCH₃

A.1.549 H OCH₃

A.1.550 H OCH₃ CH(CH₃)₂CH₂SCH₃ A.1.551 H OCH₃ CH(CH₃)₂CH₂S(O)CH₃ A.1.552H OCH₃ CH(CH₃)₂CH₂S(O)₂CH₃ A.1.553 C≡CH OCH₃ H A.1.554 C≡CH OCH₃ CH₃A.1.555 C≡CH OCH₃ CH₂CH₃ A.1.556 C≡CH OCH₃ CH(CH₃)CH₃ A.1.557 C≡CH OCH₃C(CH₃)(CH₃)CH₃ A.1.558 C≡CH OCH₃

A.1.559 C≡CH OCH₃

A.1.560 C≡CH OCH₃

A.1.561 C≡CH OCH₃

A.1.562 C≡CH OCH₃ CH(CH₃)₂CH₂SCH₃ A.1.563 C≡CH OCH₃ CH(CH₃)₂CH₂S(O)CH₃A.1.564 C≡CH OCH₃ CH(CH₃)₂CH₂S(O)₂CH₃

TABLE 1 This table discloses the 564 compounds T1.1.1 to T1.1.564 of theformula (T1)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A. For example, the specific compound T1.1.23 isthe compound of the formula T1, in which each of the variables R_(1a),R₂₀ and R₁₀₀ has the specific meaning given in the line A.1.23 of theTable A. According to the same system, also all of the other 564specific compounds disclosed in the Table 1 as well as all of thespecific compounds disclosed in the Tables 2 to 103 are specifiedanalogously.

TABLE 2 This table discloses the 564 compounds T2.1.1 to T2.1.564 of theformula (T2)

in which, for each of these 564 specific compounds, each of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 3 This table discloses the 564 compounds T3.1.1 to T3.1.564 of theformula (T3)

in which, for each of these 564 specific compounds, each of the of thevariables, R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 4 This table discloses the 564 compounds T4.1.1 to T4.1.564 of theformula (T4)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 5 This table discloses the 564 compounds T5.1.1 to T5.1.564 of theformula (T5)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 6 This table discloses the 564 compounds T6.1.1 to T6.1.564 of theformula (T6)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 7 This table discloses the 564 compounds T7.1.1 to T7.1.564 of theformula (T7)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 8 This table discloses the 564 compounds T8.1.1 to T8.1.564 of theformula (T8)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 9 This table discloses the 564 compounds T9.1.1 to T9.1.564 of theformula (T9)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 10 This table discloses the 564 compounds T10.1.1 to T10.1.564 ofthe formula (T10)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 11 This table discloses the 564 compounds T11.1.1 to T11.1.564 ofthe formula (T11)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 12 This table discloses the 564 compounds T12.1.1 to T12.1.564 ofthe formula (T12)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 13 This table discloses the 564 compounds T13.1.1 to T13.1.564 ofthe formula (T13)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 14 This table discloses the 564 compounds T14.1.1 to T14.1.564 ofthe formula (T14)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 15 This table discloses the 564 compounds T15.1.1 to T15.1.564 ofthe formula (T15)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 16 This table discloses the 564 compounds T16.1.1 to T16.1.564 ofthe formula (T16)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 17 This table discloses the 564 compounds T17.1.1 to T17.1.564 ofthe formula (T17)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 18 This table discloses the 564 compounds T18.1.1 to T18.1.564 ofthe formula (T18)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 19 This table discloses the 564 compounds T19.1.1 to T19.1.564 ofthe formula (T19)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 20 This table discloses the 564 compounds T20.1.1 to T20.1.564 ofthe formula (T20)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 21 This table discloses the 564 compounds T21.1.1 to T21.1.564 ofthe formula (T21)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 22 This table discloses the 564 compounds T22.1.1 to T22.1.564 ofthe formula (T22)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 23 This table discloses the 564 compounds T23.1.1 to T23.1.564 ofthe formula (T23)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 24 This table discloses the 564 compounds T24.1.1 to T24.1.564 ofthe formula (T24)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 25 This table discloses the 564 compounds T25.1.1 to T25.1.564 ofthe formula (T25)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 26 This table discloses the 564 compounds T26.1.1 to T26.1.564 ofthe formula (T26)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 27 This table discloses the 564 compounds T27.1.1 to T27.1.564 ofthe formula (T27)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 28 This table discloses the 564 compounds T28.1.1 to T28.1.564 ofthe formula (T28)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 29 This table discloses the 564 compounds T29.1.1 to T29.1.564 ofthe formula (T29)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 30 This table discloses the 564 compounds T30.1.1 to T30.1.564 ofthe formula (T30)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 31 This table discloses the 564 compounds T31.1.1 to T31.1.564 ofthe formula (T31)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 32 This table discloses the 564 compounds T32.1.1 to T32.1.564 ofthe formula (T32)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 33 This table discloses the 564 compounds T33.1.1 to T33.1.564 ofthe formula (T33)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 34 This table discloses the 564 compounds T34.1.1 to T34.1.564 ofthe formula (T34)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 35 This table discloses the 564 compounds T35.1.1 to T35.1.564 ofthe formula (T35)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 36 This table discloses the 564 compounds T36.1.1 to T36.1.525 ofthe formula (T36)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 37 This table discloses the 564 compounds T37.1.1 to T37.1.564 ofthe formula (T37)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 38 This table discloses the 564 compounds T38.1.1 to T38.1.564 ofthe formula (T38)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 39 This table discloses the 564 compounds T39.1.1 to T39.1.564 ofthe formula (T39)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 40 This table discloses the 564 compounds T40.1.1 to T40.1.564 ofthe formula (T40)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 41 This table discloses the 564 compounds T41.1.1 to T41.1.564 ofthe formula (T41)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 42 This table discloses the 564 compounds T42.1.1 to T42.1.564 ofthe formula (T42)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 43 This table discloses the 564 compounds T43.1.1 to T43.1.564 ofthe formula (T43)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 44 This table discloses the 564 compounds T44.1.1 to T44.1.564 ofthe formula (T44)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 45 This table discloses the 564 compounds T45.1.1 to T45.1.564 ofthe formula (T45)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 46 This table discloses the 564 compounds T46.1.1 to T46.1.564 ofthe formula (T46)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 47 This table discloses the 564 compounds T47.1.1 to T47.1.564 ofthe formula (T47)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 48 This table discloses the 564 compounds T48.1.1 to T48.1.564 ofthe formula (T48)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 49 This table discloses the 564 compounds T49.1.1 to T49.1.564 ofthe formula (T49)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 50 This table discloses the 564 compounds T50.1.1 to T50.1.564 ofthe formula (T50)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 51 This table discloses the 564 compounds T51.1.1 to T51.1.564 ofthe formula (T51)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 52 This table discloses the 564 compounds T52.1.1 to T52.1.564 ofthe formula (T52)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 53 This table discloses the 564 compounds T53.1.1 to T53.1.564 ofthe formula (T53)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 54 This table discloses the 564 compounds T54.1.1 to T54.1.564 ofthe formula (T54)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 55 This table discloses the 564 compounds T55.1.1 to T55.1.564 ofthe formula (T55)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 56 This table discloses the 564 compounds T56.1.1 to T56.1.564 ofthe formula (T56)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 57 This table discloses the 564 compounds T57.1.1 to T57.1.564 ofthe formula (T57)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 58 This table discloses the 564 compounds T58.1.1 to T58.1.564 ofthe formula (T58)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 59 This table discloses the 564 compounds T59.1.1 to T59.1.564 ofthe formula (T59)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 60 This table discloses the 564 compounds T60.1.1 to T60.1.564 ofthe formula (T60)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 61 This table discloses the 564 compounds T61.1.1 to T61.1.564 ofthe formula (T61)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 62 This table discloses the 564 compounds T62.1.1 to T62.1.564 ofthe formula (T62)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 63 This table discloses the 564 compounds T63.1.1 to T63.1.564 ofthe formula (T63)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 64 This table discloses the 564 compounds T64.1.1 to T64.1.564 ofthe formula (T64)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 65 This table discloses the 564 compounds T65.1.1 to T65.1.564 ofthe formula (T65)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 66 This table discloses the 564 compounds T66.1.1 to T66.1.564 ofthe formula (T66)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 67 This table discloses the 564 compounds T67.1.1 to T67.1.564 ofthe formula (T67)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 68 This table discloses the 564 compounds T68.1.1 to T68.1.564 ofthe formula (T68)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 69 This table discloses the 564 compounds T69.1.1 to T69.1.564 ofthe formula (T69)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 70 This table discloses the 564 compounds T70.1.1 to T70.1.564 ofthe formula (T70)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 71 This table discloses the 564 compounds T71.1.1 to T71.1.564 ofthe formula (T71)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 72 This table discloses the 564 compounds T72.1.1 to T72.1.564 ofthe formula (T72)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a)R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 73 This table discloses the 564 compounds T73.1.1 to T73.1.564 ofthe formula (T73)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 74 This table discloses the 564 compounds T74.1.1 to T74.1.564 ofthe formula (T74)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 75 This table discloses the 564 compounds T75.1.1 to T75.1.564 ofthe formula (T75)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 76 This table discloses the 564 compounds T76.1.1 to T76.1.564 ofthe formula (T76)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 77 This table discloses the 564 compounds T77.1.1 to T77.1.564 ofthe formula (T77)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 78 This table discloses the 564 compounds T78.1.1 to T78.1.564 ofthe formula (T78)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 79 This table discloses the 564 compounds T79.1.1 to T79.1.564 ofthe formula (T79)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 80 This table discloses the 564 compounds T80.1.1 to T80.1.564 ofthe formula (T80)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the table A.

TABLE 81 This table discloses the 564 compounds T81.1.1 to T81.1.564 ofthe formula (T81)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 82 This table discloses the 564 compounds T82.1.1 to T82.1.564 ofthe formula (T82)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding lines, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 83 This table discloses the 564 compounds T83.1.1 to T83.1.564 ofthe formula (T83)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 84 This table discloses the 564 compounds T84.1.1 to T84.1.564 ofthe formula (T84)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 85 This table discloses the 564 compounds T85.1.1 to T85.1.564 ofthe formula (T85)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 86 This table discloses the 564 compounds T86.1.1 to T86.1.564 ofthe formula (T86)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 87 This table discloses the 564 compounds T87.1.1 to T87.1.564 ofthe formula (T87)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 88 This table discloses the 564 compounds T88.1.1 to T88.1.564 ofthe formula (T88)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 89 This table discloses the 564 compounds T89.1.1 to T89.1.564 ofthe formula (T89)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 90 This table discloses the 564 compounds T90.1.1 to T90.1.564 ofthe formula (T90)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 91 This table discloses the 564 compounds T91.1.1 to T91.1.564 ofthe formula (T91)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 92 This table discloses the 564 compounds T92.1.1 to T92.1.564 ofthe formula (T92)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 93 This table discloses the 564 compounds T93.1.1 to T93.1.564 ofthe formula (T93)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 94 This table discloses the 564 compounds T94.1.1 to T94.1.564 ofthe formula (T94)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 95 This table discloses the 564 compounds T95.1.1 to T95.1.564 ofthe formula (T95)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriatety selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 96 This table discloses the 564 compounds T96.1.1 to T96.1.564 ofthe formula (T96)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 97 This table discloses the 564 compounds T97.1.1 to T97.1.564 ofthe formula (T97)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 98 This table discloses the 564 compounds T98.1.1 to T98.1.564 ofthe formula (T98)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

TABLE 99 This table discloses the 564 compounds T99.1.1 to T99.1.564 ofthe formula (T99)

in which, for each of these 564 specific compounds, each of the of thevariables R_(1a), R₂₀ and R₁₀₀ has the specific meaning given in thecorresponding line, appropriately selected from the 564 lines A.1.1 toA.1.564 of the Table A.

Formulation examples (%=percent by weight)

Example F1: Emulsion concentrates a) b) c) Active ingredient 25% 40% 50%Calcium dodecylbenzenesulfonate  5%  8%  6% Castor oil polyethyleneglycol ether  5% — — (36 mol of EO) Tributylphenoxypolyethylene glycolether — 12%  4% (30 mol of EO) Cyclohexanone — 15% 20% Xylene mixture65% 25% 20%

Emulsions of any desired concentration can be prepared from suchconcentrates by dilution with water.

Example F2: Solutions a) b) c) d) Active ingredient 80% 10% 5% 95%Ethylene glycol monomethyl ether 20% — — — Polyethylene glycol MW 400 —70% — — N-Methylpyrrolid-2-one — 20% — — Epoxidized coconut oil — — 1% 5% Petroleum ether (boiling range: 160-190°) — — 94%  —

The solutions are suitable for use in the form of microdrops.

Example F3: Granules a) b) c) d) Active ingredient 5% 10%  8% 21% Kaolin94%  — 79% 54% Highly disperse silica 1% — 13% 7% Attapulgite — 90% —18%

The active ingredient is dissolved in dichloromethane, the solution issprayed onto the carrier(s), and the solvent is subsequently evaporatedin vacuo.

Example F4: Dusts a) b) Active ingredient 2% 5% Highly disperse silica1% 5% Talc 97%  — Kaolin — 90% 

Ready-to-use dusts are obtained by intimately mixing the carriers andthe active ingredient.

Example F5: Wettable powders a) b) c) Active ingredient 25%  50% 75%Sodium lignosulfonate 5%  5% — Sodium lauryl sulfate 3% —  5% Sodiumdiisobutylnaphthalenesulfonate —  6% 10% Octylphenoxypolyethylene glycol—  2% — ether (7-8 mol of EO) Highly disperse silica 5% 10% 10% Kaolin62%  27% —

The active ingredient is mixed with the additives and the mixture isground thoroughly in a suitable mill. This gives wettable powders, whichcan be diluted with water to give suspensions of any desiredconcentration.

Example F6 Extruder Granules

Active ingredient 10% Sodium lignosulfonate 2% Carboxymethylcellulose 1%Kaolin 87%

The active ingredient is mixed with the additives, and the mixture isground, moistened with water, extruded, granulated and dried in a streamof air.

Example F7 Coated Granules

Active ingredient 3% Polyethylene glycol (MW 200) 3% Kaolin 94%

In a mixer, the finely ground active ingredient is applied uniformly tothe kaolin, which has been moistened with the polyethylene glycol. Thisgives dust-free coated granules.

Example F8 Suspension Concentrate

Active ingredient 40% Ethylene glycol 10% Nonylphenoxypolyethyleneglycol ether (15 mol of EO) 6% Sodium lignosulfonate 10%Carboxymethylcellulose 1% 37% aqueous formaldehyde solution 0.2%Silicone oil (75% aqueous emulsion) 0.8% Water 32%

The finely ground active ingredient is mixed intimately with theadditives. Suspensions of any desired concentration can be prepared fromthe thus resulting suspension concentrate by dilution with water.

The activity of the compositions according to the invention can bebroadened considerably, and adapted to prevailing circumstances, byadding other insecticidally, acaricidally and/or fungicidally activeingredients. The mixtures of the compounds of formula I with otherinsecticidally, acaricidally and/or fungicidally active ingredients mayalso have further surprising advantages which can also be described, ina wider sense, as synergistic activity. For example, better tolerance byplants, reduced phytotoxicity, insects can be controlled in theirdifferent development stages or better behaviour during theirproduction, for example during grinding or mixing, during their storageor during their use.

Suitable additions to active ingredients here are, for example,representatives of the following classes of active ingredients:organophosphorus compounds, nitrophenol derivatives, thioureas, juvenilehormones, formamidines, benzophenone derivatives, ureas, pyrrolederivatives, carbamates, pyrethroids, chlorinated hydrocarbons,acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoidsand Bacillus thuringiensis preparations.

The following mixtures of the compounds of formula I with activeingredients are preferred (the abbreviation “TX” means “one compoundselected from the group consisting of the compounds of formulae T1 toT99 described in tables 1 to 97 of the present invention”):

-   -   an adjuvant selected from the group of substances consisting of        petroleum oils (alternative name) (628)+TX,    -   an acaricide selected from the group of substances consisting of        1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910)+TX,        2,4-dichlorophenyl benzenesulfonate (IUPAC/Chemical Abstracts        name) (1059)+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC        name) (1295)+TX, 4-chlorophenyl phenyl sulfone (IUPAC name)        (981)+TX, abamectin (1)+TX, acequinocyl (3)+TX, acetoprole        [CCN]+TX, acrinathrin (9)+TX, aldicarb (16)+TX, aldoxycarb        (863)+TX, alpha-cypermethrin (202)+TX, amidithion (870)+TX,        amidoflumet [CCN]+TX, amidothioate (872)+TX, amiton (875)+TX,        amiton hydrogen oxalate (875)+TX, amitraz (24)+TX, aramite        (881)+TX, arsenous oxide (882)+TX, AVI 382 (compound code)+TX,        AZ 60541 (compound code)+TX, azinphos-ethyl (44)+TX,        azinphos-methyl (45)+TX, azobenzene (IUPAC name) (888)+TX,        azocyclotin (46)+TX, azothoate (889)+TX, benomyl (62)+TX,        benoxafos (alternative name) [CCN]+TX, benzoximate (71)+TX,        benzyl benzoate (IUPAC name) [CCN]+TX, bifenazate (74)+TX,        bifenthrin (76)+TX, binapacryl (907)+TX, brofenvalerate        (alternative name)+TX, bromocyclen (918)+TX, bromophos (920)+TX,        bromophos-ethyl (921)+TX, bromopropylate (94)+TX, buprofezin        (99)+TX, butocarboxim (103)+TX, butoxycarboxim (104)+TX,        butylpyridaben (alternative name)+TX, calcium polysulfide (IUPAC        name) (111)+TX, camphechlor (941)+TX, carbanolate (943)+TX,        carbaryl (115)+TX, carbofuran (118)+TX, carbophenothion        (947)+TX, CGA 50′439 (development code) (125)+TX, chinomethionat        (126)+TX, chlorbenside (959)+TX, chlordimeform (964)+TX,        chlordimeform hydrochloride (964)+TX, chlorfenapyr (130)+TX,        chlorfenethol (968)+TX, chlorfenson (970)+TX, chiorfensulphide        (971)+TX, chlorfenvinphos (131)+TX, chlorobenzilate (975)+TX,        chloromebuform (977)+TX, chloromethiuron (978)+TX,        chloropropylate (983)+TX, chlorpyrifos (145)+TX,        chlorpyrifos-methyl (146)+TX, chlorthiophos (994)+TX, cinerin I        (696)+TX, cinerin II (696)+TX, cinerins (696)+TX, clofentezine        (158)+TX, closantel (alternative name) [CCN]+TX, coumaphos        (174)+TX, crotamiton (alternative name) [CCN]+TX, crotoxyphos        (1010)+TX, cufraneb (1013)+TX, cyanthoate (1020)+TX,        cyflumetofen (CAS Reg. No.: 400882-07-7)+TX, cyhalothrin        (196)+TX, cyhexatin (199)+TX, cypermethrin (201)+TX, DCPM        (1032)+TX, DDT (219)+TX, demephion (1037)+TX, demephion-O        (1037)+TX, demephion-S (1037)+TX, demeton (1038)+TX,        demeton-methyl (224)+TX, demeton-O (1038)+TX, demeton-O-methyl        (224)+TX, demeton-S (1038)+TX, demeton-S-methyl (224)+TX,        demeton-Smethylsulphon (1039)+TX, diafenthiuron (226)+TX,        dialifos (1042)+TX, diazinon (227)+TX, dichlofluanid (230)+TX,        dichlorvos (236)+TX, dicliphos (alternative name)+TX, dicofol        (242)+TX, dicrotophos (243)+TX, dienochlor (1071)+TX, dimefox        (1081)+TX, dimethoate (262)+TX, dinactin (alternative name)        (653)+TX, dinex (1089)+TX, dinex-diclexine (1089)+TX, dinobuton        (269)+TX, dinocap (270)+TX, dinocap-4 [CCN]+TX, dinocap-6        [CCN]+TX, dinocton (1090)+TX, dinopenton (1092)+TX, dinosulfon        (1097)+TX, dinoterbon (1098)+TX, dioxathion (1102)+TX, diphenyl        sulfone (IUPAC name) (1103)+TX, disulfuram (alternative name)        [CCN]+TX, disulfoton (278)+TX, DNOC (282)+TX, dofenapyn        (1113)+TX, doramectin (alternative name) [CCN]+TX, endosulfan        (294)+TX, endothion (1121)+TX, EPN (297)+TX, eprinomectin        (alternative name) [CCN]+TX, ethion (309)+TX, ethoate-methyl        (1134)+TX, etoxazole (320)+TX, etrimfos (1142)+TX, fenazaflor        (1147)+TX, fenazaquin (328)+TX, fenbutatin oxide (330)+TX,        fenothiocarb (337)+TX, fenpropathrin (342)+TX, fenpyrad        (alternative name)+TX, fenpyroximate (345)+TX, fenson (1157)+TX,        fentrifanil (1161)+TX, fenvalerate (349)+TX, fipronil (354)+TX,        fluacrypyrim (360)+TX, fluazuron (1166)+TX, flubenzimine        (1167)+TX, flucycloxuron (366)+TX, flucythrinate (367)+TX,        fluenetil (1169)+TX, flufenoxuron (370)+TX, flumethrin (372)+TX,        fluorbenside (1174)+TX, fluvalinate (1184)+TX, FMC 1137        (development code) (1185)+TX, formetanate (405)+TX, formetanate        hydrochloride (405)+TX, formothion (1192)+TX, formparanate        (1193)+TX, gamma-HCH (430)+TX, glyodin (1205)+TX, halfenprox        (424)+TX, heptenophos (432)+TX, hexadecyl        cyclopropanecarboxylate (IUPAC/Chemical Abstracts name)        (1216)+TX, hexythiazox (441)+TX, iodomethane (IUPAC name)        (542)+TX, isocarbophos (alternative name) (473)+TX, isopropyl        O-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473)+TX,        ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX,        jasmolin II (696)+TX, jodfenphos (1248)+TX, lindane (430)+TX,        lufenuron (490)+TX, malathion (492)+TX, malonoben (1254)+TX,        mecarbam (502)+TX, mephosfolan (1261)+TX, mesulfen (alternative        name) [CCN]+TX, methacrifos (1266)+TX, methamidophos (527)+TX,        methidathion (529)+TX, methiocarb (530)+TX, methomyl (531)+TX,        methyl bromide (537)+TX, metolcarb (550)+TX, mevinphos (556)+TX,        mexacarbate (1290)+TX, milbemectin (557)+TX, milbemycin oxime        (alternative name) [CCN]+TX, mipafox (1293)+TX, monocrotophos        (561)+TX, morphothion (1300)+TX, moxidectin (alternative name)        [CCN]+TX, naled (567)+TX, NC-184 (compound code)+TX, NC-512        (compound code)+TX, nifluridide (1309)+TX, nikkomycins        (alternative name) [CCN]+TX, nitrilacarb (1313)+TX, nitrilacarb        1:1 zinc chloride complex (1313)+TX, NNI-0101 (compound        code)+TX, NNI-0250 (compound code)+TX, omethoate (594)+TX,        oxamyl (602)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX,        pp′-DDT (219)+TX, parathion (615)+TX, permethrin (626)+TX,        petroleum oils (alternative name) (628)+TX, phenkapton        (1330)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone        (637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosphamidon        (639)+TX, phoxim (642)+TX, pirimiphos-methyl (652)+TX,        polychloroterpenes (traditional name) (1347)+TX, polynactins        (alternative name) (653)+TX, proclonol (1350)+TX, profenofos        (662)+TX, promacyl (1354)+TX, propargite (671)+TX, propetamphos        (673)+TX, propoxur (678)+TX, prothidathion (1360)+TX, prothoate        (1362)+TX, pyrethrin I (696)+TX, pyrethrin II (696)+TX,        pyrethrins (696)+TX, pyridaben (699)+TX, pyridaphenthion        (701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, quinalphos        (711)+TX, quintiofos (1381)+TX, R-1492 (development code)        (1382)+TX, RA-17 (development code) (1383)+TX, rotenone        (722)+TX, schradan (1389)+TX, sebufos (alternative name)+TX,        selamectin (alternative name) [CCN]+TX, SI-0009 (compound        code)+TX, sophamide (1402)+TX, spirodiclofen (738)+TX,        spiromesifen (739)+TX, SSI-121 (development code) (1404)+TX,        sulfuram (alternative name) [CCN]+TX, sulfluramid (750)+TX,        sulfotep (753)+TX, sulfur (754)+TX, SZI-121 (development code)        (757)+TX, tau-fluvalinate (398)+TX, tebufenpyrad (763)+TX, TEPP        (1417)+TX, terbam (alternative name)+TX, tetrachlorvinphos        (777)+TX, tetradifon (786)+TX, tetranactin (alternative name)        (653)+TX, tetrasul (1425)+TX, thiafenox (alternative name)+TX,        thiocarboxime (1431)+TX, thiofanox (800)+TX, thiometon (801)+TX,        thioquinox (1436)+TX, thuringiensin (alternative name) [CCN]+TX,        triamiphos (1441)+TX, triarathene (1443)+TX, triazophos        (820)+TX, triazuron (alternative name)+TX, trichlorfon (824)+TX,        trifenofos (1455)+TX, trinactin (alternative name) (653)+TX,        vamidothion (847)+TX, vaniliprole [CCN] and Yl-5302 (compound        code)+TX,

an algicide selected from the group of substances consisting ofbethoxazin [CCN]+TX, copper dioctanoate (IUPAC name) (170)+TX, coppersulfate (172)+TX, cybutryne [CCN]+TX, dichlone (1052)+TX, dichlorophen(232)+TX, endothal (295)+TX, fentin (347)+TX, hydrated lime [CCN]+TX,nabam (566)+TX, quinoclamine (714)+TX, quinonamid (1379)+TX, simazine(730)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltinhydroxide (IUPAC name) (347)+TX,

an anthelmintic selected from the group of substances consisting ofabamectin (1)+TX, crufomate (1011)+TX, doramectin (alternative name)[CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, eprinomectin(alternative name) [CCN]+TX, ivermectin (alternative name) [CCN]+TX,milbemycin oxime (alternative name) [CCN]+TX, moxidectin (alternativename) [CCN]+TX, piperazine [CCN]+TX, selamectin (alternative name)[CCN]+TX, spinosad (737) and thiophanate (1435)+TX,

an avicide selected from the group of substances consisting ofchloralose (127)+TX, endrin (1122)+TX, fenthion (346)+TX,pyridin-4-amine (IUPAC name) (23) and strychnine (745)+TX,

a bactericide selected from the group of substances consisting of1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,8-hydroxyquinoline sulfate (446)+TX, bronopol (97)+TX, copperdioctanoate (IUPAC name) (170)+TX, copper hydroxide (IUPAC name)(169)+TX, cresol [CCN]+TX, dichlorophen (232)+TX, dipyrithione(1105)+TX, dodicin (1112)+TX, fenaminosulf (1144)+TX, formaldehyde(404)+TX, hydrargaphen (alternative name) [CCN]+TX, kasugamycin(483)+TX, kasugamycin hydrochloride hydrate (483)+TX, nickelbis(dimethyldithiocarbamate) (IUPAC name) (1308)+TX, nitrapyrin(580)+TX, octhilinone (590)+TX, oxolinic acid (606)+TX, oxytetracycline(611)+TX, potassium hydroxyquinoline sulfate (446)+TX, probenazole(658)+TX, streptomycin (744)+TX, streptomycin sesquisulfate (744)+TX,tecloftalam (766)+TX, and thiomersal (alternative name) [CCN]+TX,

a biological agent selected from the group of substances consisting ofAdoxophyes orana GV (alternative name) (12)+TX, Agrobacteriumradiobacter (alternative name) (13)+TX, Amblyseius spp. (alternativename) (19)+TX, Anagrapha falcifera NPV (alternative name) (28)+TX,Anagrus atomus (alternative name) (29)+TX, Aphelinus abdominalis(alternative name) (33)+TX, Aphidius colemani (alternative name)(34)+TX, Aphidoletes aphidimyza (alternative name) (35)+TX, Autographacalifornica NPV (alternative name) (38)+TX, Bacillus firmus (alternativename) (48)+TX, Bacillus sphaericus Neide (scientific name) (49)+TX,Bacillus thuringiensis Berliner (scientific name) (51)+TX, Bacillusthuringiensis subsp. aizawai (scientific name) (51)+TX, Bacillusthuringiensis subsp. israelensis (scientific name) (51)+TX, Bacillusthuringiensis subsp. japonensis (scientific name) (51)+TX, Bacillusthuringiensis subsp. kurstaki (scientific name) (51)+TX, Bacillusthuringiensis subsp. tenebrionis (scientific name) (51)+TX, Beauveriabassiana (alternative name) (53)+TX, Beauveria brongniartii (alternativename) (54)+TX, Chrysoperla carnea (alternative name) (151)+TX,Cryptolaemus montrouzieri (alternative name) (178)+TX, Cydia pomonellaGV (alternative name) (191)+TX, Dacnusa sibirica (alternative name)(212)+TX, Diglyphus isaea (alternative name) (254)+TX, Encarsia formosa(scientific name) (293)+TX, Eretmocerus eremicus (alternative name)(300)+TX, Helicoverpa zea NPV (alternative name) (431)+TX,Heterorhabditis bacteriophora and H. megidis (alternative name)(433)+TX, Hippodamia convergens (alternative name) (442)+TX, Leptomastixdactylopii (alternative name) (488)+TX, Macrolophus caliginosus(alternative name) (491)+TX, Mamestra brassicae NPV (alternative name)(494)+TX, Metaphycus helvolus (alternative name) (522)+TX, Metarhiziumanisopliae var. acridum (scientific name) (523)+TX, Metarhiziumanisopliae var. anisopliae (scientific name) (523)+TX, Neodiprionsertifer NPV and N. lecontei NPV (alternative name) (575)+TX, Orius spp.(alternative name) (596)+TX, Paecilomyces fumosoroseus (alternativename) (613)+TX, Phytoseiulus persimilis (alternative name) (644)+TX,Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientificname) (741)+TX, Steinernema bibionis (alternative name) (742)+TX,Steinernema carpocapsae (alternative name) (742)+TX, Steinernema feltiae(alternative name) (742)+TX, Steinernema glaseri (alternative name)(742)+TX, Steinernema riobrave (alternative name) (742)+TX, Steinernemariobravis (alternative name) (742)+TX, Steinernema scapterisci(alternative name) (742)+TX, Steinernema spp. (alternative name)(742)+TX, Trichogramma spp. (alternative name) (826)+TX, Typhlodromusoccidentalis (alternative name) (844) and Verticillium lecanii(alternative name) (848)+TX,

a soil sterilant selected from the group of substances consisting ofiodomethane (IUPAC name) (542) and methyl bromide (537)+TX,

a chemosterilant selected from the group of substances consisting ofapholate [CCN]+TX, bisazir (alternative name) [CCN]+TX, busulfan(alternative name) [CCN]+TX, diflubenzuron (250)+TX, dimatif(alternative name) [CCN]+TX, hemel [CCN]+TX, hempa [CCN]+TX, metepa[CCN]+TX, methiotepa [CCN]+TX, methyl apholate [CCN]+TX, morzid[CCN]+TX, penfluoron (alternative name) [CCN]+TX, tepa [CCN]+TX,thiohempa (alternative name) [CCN]+TX, thiotepa (alternative name)[CCN]+TX, tretamine (alternative name) [CCN] and uredepa (alternativename) [CCN]+TX,

an insect pheromone selected from the group of substances consisting of(E)-dec-5-en-1-yl acetate with (E)-dec-S-en-1-ol (IUPAC name) (222)+TX,(E)-tridec-4-en-1-yl acetate (IUPAC name) (829)+TX,(E)-6-methylhept-2-en-4-ol (IUPAC name) (541)+TX,(E,Z)-tetradeca-4,10-dien-1-yl acetate (IUPAC name) (779)+TX,(Z)-dodec-7-en-1-yl acetate (IUPAC name) (285)+TX, (Z)-hexadec-11-enal(IUPAC name) (436)+TX, (Z)hexadec-11-en-1-yl acetate (IUPAC name)(437)+TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438)+TX,(Z)-icos-13-en-10-one (IUPAC name) (448)+TX, (Z)tetradec-7-en-1-al(IUPAC name) (782)+TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783)+TX,(Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784)+TX,(7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283)+TX,(9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780)+TX,(9Z,12E)-tetradeca-9,12-dien-1-yl acetate (IUPAC name) (781)+TX,14-methyloctadec-1-ene (IUPAC name) (545)+TX, 4-methylnonan-5-ol with4-methylnonan-5-one (IUPAC name) (544)+TX, alpha-multistriatin(alternative name) [CCN]+TX, brevicomin (alternative name) [CCN]+TX,codlelure (alternative name) [CCN]+TX, codlemone (alternative name)(167)+TX, cuelure (alternative name) (179)+TX, disparlure (277)+TX,dodec-8-en-1-yl acetate (IUPAC name) (286)+TX, dodec-9-en-1-yl acetate(IUPAC name) (287)+TX, dodeca-8+TX, 10-dien-1-yl acetate (IUPAC name)(284)+TX, dominicalure (alternative name) [CCN]+TX, ethyl4-methyloctanoate (IUPAC name) (317)+TX, eugenol (alternative name)[CCN]+TX, frontalin (alternative name) [CCN]+TX, gossyplure (alternativename) (420)+TX, grandlure (421)+TX, grandlure I (alternative name)(421)+TX, grandlure II (alternative name) (421)+TX, grandlure III(alternative name) (421)+TX, grandlure IV (alternative name) (421)+TX,hexylure [CCN]+TX, ipsdienol (alternative name) [CCN]+TX, ipsenol(alternative name) [CCN]+TX, japonilure (alternative name) (481)+TX,lineatin (alternative name) [CCN]+TX, litlure (alternative name)[CCN]+TX, looplure (alternative name) [CCN]+TX, medlure [CCN]+TX,megatomoic acid (alternative name) [CCN]+TX, methyl eugenol (alternativename) (540)+TX, muscalure (563)+TX, octadeca-2,13-dien-1-yl acetate(IUPAC name) (588)+TX, octadeca-3,13-dien-1-yl acetate (IUPAC name)(589)+TX, orfralure (alternative name) [CCN]+TX, oryctalure (alternativename) (317)+TX, ostramone (alternative name) [CCN]+TX, siglure [CCN]+TX,sordidin (alternative name) (736)+TX, sulcatol (alternative name)[CCN]+TX, tetradec-11-en-1-yl acetate (IUPAC name) (785)+TX, trimedlure(839)+TX, trimedlure A (alternative name) (839)+TX, trimedlure B₁(alternative name) (839)+TX, trimedlure B₂ (alternative name) (839)+TX,trimedlure C (alternative name) (839) and trunc-call (alternative name)[CCN]+TX, an insect repellent selected from the group of substancesconsisting of 2-(octylthio)ethanol (IUPAC name) (591)+TX, butopyronoxyl(933)+TX, butoxy(polypropylene glycol) (936)+TX, dibutyl adipate (IUPACname) (1046)+TX, dibutyl phthalate (1047)+TX, dibutyl succinate (IUPACname) (1048)+TX, diethyltoluamide [CCN]+TX, dimethyl carbate [CCN]+TX,dimethyl phthalate [CCN]+TX, ethyl hexanediol (1137)+TX, hexamide[CCN]+TX, methoquin-butyl (1276)+TX, methylneodecanamide [CCN]+TX,oxamate [CCN] and picaridin [CCN]+TX,

an insecticide selected from the group of substances consisting of1-dichloro-1-nitroethane (IUPAC/Chemical Abstracts name) (1058)+TX,1,1-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), +TX,1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062)+TX,1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063)+TX,1-bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916)+TX,2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name)(1451)+TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate(IUPAC name) (1066)+TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate(IUPAC/Chemical Abstracts name) (1109)+TX, 2-(2-butoxyethoxy)ethylthiocyanate (IUPAC/Chemical Abstracts name) (935)+TX,2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/ChemicalAbstracts name) (1084)+TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name)(986)+TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984)+TX,2-imidazolidone (IUPAC name) (1225)+TX, 2-isovalerylindan-1,3-dione(IUPAC name) (1246)+TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate(IUPAC name) (1284)+TX, 2-thiocyanatoethyl laurate (IUPAC name)(1433)+TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917)+TX,3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283)+TX,4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name)(1285)+TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPACname) (1085)+TX, abamectin (1)+TX, acephate (2)+TX, acetamiprid (4)+TX,acethion (alternative name) [CCN]+TX, acetoprole [CCN]+TX, acrinathrin(9)+TX, acrylonitrile (IUPAC name) (861)+TX, alanycarb (15)+TX, aldicarb(16)+TX, aldoxycarb (863)+TX, aldrin (864)+TX, allethrin (17)+TX,allosamidin (alternative name) [CCN]+TX, allyxycarb (866)+TX,alpha-cypermethrin (202)+TX, alpha-ecdysone (alternative name) [CCN]+TX,aluminium phosphide (640)+TX, amidithion (870)+TX, amidothioate(872)+TX, aminocarb (873)+TX, amiton (875)+TX, amiton hydrogen oxalate(875)+TX, amitraz (24)+TX, anabasine (877)+TX, athidathion (883)+TX, AVI382 (compound code)+TX, AZ 60541 (compound code)+TX, azadirachtin(alternative name) (41)+TX, azamethiphos (42)+TX, azinphos-ethyl(44)+TX, azinphos-methyl (45)+TX, azothoate (889)+TX, Bacillusthuringiensis delta endotoxins (alternative name) (52)+TX, bariumhexafluorosilicate (alternative name) [CCN]+TX, barium polysulfide(IUPAC/Chemical Abstracts name) (892)+TX, barthrin [CCN]+TX, Bayer22/190 (development code) (893)+TX, Bayer 22408 (development code)(894)+TX, bendiocarb (58)+TX, benfuracarb (60)+TX, bensultap (66)+TX,beta-cyfluthrin (194)+TX, betacypermethrin (203)+TX, bifenthrin (76)+TX,bioallethrin (78)+TX, bioallethrin Scyclopentenyl isomer (alternativename) (79)+TX, bioethanomethrin [CCN]+TX, biopermethrin (908)+TX,bioresmethrin (80)+TX, bis(2-chloroethyl)ether (IUPAC name) (909)+TX,bistrifluoron (83)+TX, borax (86)+TX, brofenvalerate (alternativename)+TX, bromfenvinfos (914)+TX, bromocyclen (918)+TX, bromo-DDT(alternative name) [CCN]+TX, bromophos (920)+TX, bromophos-ethyl(921)+TX, bufencarb (924)+TX, buprofezin (99)+TX, butacarb (926)+TX,butathiofos (927)+TX, butocarboxim (103)+TX, butonate (932)+TX,butoxycarboxim (104)+TX, butylpyridaben (alternative name)+TX, cadusafos(109)+TX, calcium arsenate [CCN]+TX, calcium cyanide (444)+TX, calciumpolysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX, carbanolate(943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbon disulfide(IUPAC/Chemical Abstracts name) (945)+TX, carbon tetrachloride (IUPACname) (946)+TX, carbophenothion (947)+TX, carbosulfan (119)+TX, cartap(123)+TX, cartap hydrochloride (123)+TX, cevadine (alternative name)(725)+TX, chlorbicyclen (960)+TX, chlordane (128)+TX, chlordecone(963)+TX, chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX,chlorethoxyfos (129)+TX, chlorfenapyr (130)+TX, chlorfenvinphos(131)+TX, chlorfluazuron (132)+TX, chlormephos (136)+TX, chloroform[CCN]+TX, chloropicrin (141)+TX, chlorphoxim (989)+TX, chlorprazophos(990)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl (146)+TX,chlorthiophos (994)+TX, chromafenozide (150)+TX, cinerin I (696)+TX,cinerin II (696)+TX, cinerins (696)+TX, cis-resmethrin (alternativename)+TX, cismethrin (80)+TX, clocythrin (alternative name)+TX,cloethocarb (999)+TX, closantel (alternative name) [CCN]+TX,clothianidin (165)+TX, copper acetoarsenite [CCN]+TX, copper arsenate[CCN]+TX, copper oleate [CCN]+TX, coumaphos (174)+TX, coumithoate(1006)+TX, crotamiton (alternative name) [CCN]+TX, crotoxyphos(1010)+TX, crufomate (1011)+TX, cryolite (alternative name) (177)+TX, CS708 (development code) (1012)+TX, cyanofenphos (1019)+TX, cyanophos(184)+TX, cyanthoate (1020)+TX, cyclethrin [CCN]+TX, cycloprothrin(188)+TX, cyfluthrin (193)+TX, cyhalothrin (196)+TX, cypermethrin(201)+TX, cyphenothrin (206)+TX, cyromazine (209)+TX, cythioate(alternative name) [CCN]+TX, d-limonene (alternative name) [CCN]+TX,d-tetramethrin (alternative name) (788)+TX, DAEP (1031)+TX, dazomet(216)+TX, DDT (219)+TX, decarbofuran (1034)+TX, deltamethrin (223)+TX,demephion (1037)+TX, demephion-O (1037)+TX, demephion-S (1037)+TX,demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O (1038)+TX,demeton-O-methyl (224)+TX, demeton-S (1038)+TX, demeton-S-methyl(224)+TX, demeton-S-methylsulphon (1039)+TX, diafenthiuron (226)+TX,dialifos (1042)+TX, diamidafos (1044)+TX, diazinon (227)+TX, dicapthon(1050)+TX, dichlofenthion (1051)+TX, dichlorvos (236)+TX, dicliphos(alternative name)+TX, dicresyl (alternative name) [CCN]+TX, dicrotophos(243)+TX, dicyclanil (244)+TX, dieldrin (1070)+TX, diethyl5-methylpyrazol-3-yl phosphate (IUPAC name) (1076)+TX, diflubenzuron(250)+TX, dilor (alternative name) [CCN]+TX, dimefluthrin [CCN]+TX,dimefox (1081)+TX, dimetan (1085)+TX, dimethoate (262)+TX, dimethrin(1083)+TX, dimethylvinphos (265)+TX, dimetilan (1086)+TX, dinex(1089)+TX, dinex-diclexine (1089)+TX, dinoprop (1093)+TX, dinosam(1094)+TX, dinoseb (1095)+TX, dinotefuran (271)+TX, diofenolan(1099)+TX, dioxabenzofos (1100)+TX, dioxacarb (1101)+TX, dioxathion(1102)+TX, disulfoton (278)+TX, dithicrofos (1108)+TX, DNOC (282)+TX,doramectin (alternative name) [CCN]+TX, DSP (1115)+TX, ecdysterone(alternative name) [CCN]+TX, EI 1642 (development code) (1118)+TX,emamectin (291)+TX, emamectin benzoate (291)+TX, EMPC (1120)+TX,empenthrin (292)+TX, endosulfan (294)+TX, endothion (1121)+TX, endrin(1122)+TX, EPBP (1123)+TX, EPN (297)+TX, epofenonane (1124)+TX,eprinomectin (alternative name) [CCN]+TX, esfenvalerate (302)+TX,etaphos (alternative name) [CCN]+TX, ethiofencarb (308)+TX, ethion(309)+TX, ethiprole (310)+TX, ethoate-methyl (1134)+TX, ethoprophos(312)+TX, ethyl formate (IUPAC name) [CCN]+TX, ethyl-DDD (alternativename) (1056)+TX, ethylene dibromide (316)+TX, ethylene dichloride(chemical name) (1136)+TX, ethylene oxide [CCN]+TX, etofenprox (319)+TX,etrimfos (1142)+TX, EXD (1143)+TX, famphur (323)+TX, fenamiphos(326)+TX, fenazaflor (1147)+TX, fenchforphos (1148)+TX, fenethacarb(1149)+TX, fenfluthrin (1150)+TX, fenitrothion (335)+TX, fenobucarb(336)+TX, fenoxacrim (1153)+TX, fenoxycarb (340)+TX, fenpirithrin(1155)+TX, fenpropathrin (342)+TX, fenpyrad (alternative name)+TX,fensulfothion (1158)+TX, fenthion (346)+TX, fenthion-ethyl [CCN]+TX,fenvalerate (349)+TX, fipronil (354)+TX, flonicamid (358)+TX,flubendiamide (CAS. Reg. No.: 272451-65-7)+TX, flucofuron (1168)+TX,flucycloxuron (366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX,flufenerim [CCN]+TX, flufenoxuron (370)+TX, flufenprox (1171)+TX,flumethrin (372)+TX, fluvalinate (1184)+TX, FMC 1137 (development code)(1185)+TX, fonofos (1191)+TX, formetanate (405)+TX, formetanatehydrochloride (405)+TX, formothion (1192)+TX, formparanate (1193)+TX,fosmethilan (1194)+TX, fospirate (1195)+TX, fosthiazate (408)+TX,fosthietan (1196)+TX, furathiocarb (412)+TX, furethrin (1200)+TX,gamma-cyhalothrin (197)+TX, gamma-HCH (430)+TX, guazatine (422)+TX,guazatine acetates (422)+TX, GY-81 (development code) (423)+TX,halfenprox (424)+TX, halofenozide (425)+TX, HCH (430)+TX, HEOD(1070)+TX, heptachlor (1211)+TX, heptenophos (432)+TX, heterophos[CCN]+TX, hexaflumuron (439)+TX, HHDN (864)+TX, hydramethylnon (443)+TX,hydrogen cyanide (444)+TX, hydroprene (445)+TX, hyquincarb (1223)+TX,imidacloprid (458)+TX, imiprothrin (460)+TX, indoxacarb (465)+TX,iodomethane (IUPAC name) (542)+TX, IPSP (1229)+TX, isazofos (1231)+TX,isobenzan (1232)+TX, isocarbophos (alternative name) (473)+TX, isodrin(1235)+TX, isofenphos (1236)+TX, isolane (1237)+TX, isoprocarb (472)+TX,isopropyl O-(methoxyaminothiophosphoryl)salicylate (IUPAC name)(473)+TX, isoprothiolane (474)+TX, isothioate (1244)+TX, isoxathion(480)+TX, ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX,jasmolin II (696)+TX, jodfenphos (1248)+TX, juvenile hormone I(alternative name) [CCN]+TX, juvenile hormone II (alternative name)[CCN]+TX, juvenile hormone III (alternative name) [CCN]+TX, kelevan(1249)+TX, kinoprene (484)+TX, lambda-cyhalothrin (198)+TX, leadarsenate [CCN]+TX, lepimectin (CCN)+TX, leptophos (1250)+TX, lindane(430)+TX, lirimfos (1251)+TX, lufenuron (490)+TX, lythidathion(1253)+TX, m-cumenyl methylcarbamate (IUPAC name) (1014)+TX, magnesiumphosphide (IUPAC name) (640)+TX, malathion (492)+TX, malonoben(1254)+TX, mazidox (1255)+TX, mecarbam (502)+TX, mecarphon (1258)+TX,menazon (1260)+TX, mephosfolan (1261)+TX, mercurous chloride (513)+TX,mesulfenfos (1263)+TX, metaflumizone (CCN)+TX, metam (519)+TX,metam-potassium (alternative name) (519)+TX, metam-sodium (519)+TX,methacrifos (1266)+TX, methamidophos (527)+TX, methanesulfonyl fluoride(IUPAC/Chemical Abstracts name) (1268)+TX, methidathion (529)+TX,methiocarb (530)+TX, methocrotophos (1273)+TX, methomyl (531)+TX,methoprene (532)+TX, methoquin-butyl (1276)+TX, methothrin (alternativename) (533)+TX, methoxychlor (534)+TX, methoxyfenozide (535)+TX, methylbromide (537)+TX, methyl isothiocyanate (543)+TX, methylchloroform(alternative name) [CCN]+TX, methylene chloride [CCN]+TX, metofluthrin[CCN]+TX, metolcarb (550)+TX, metoxadiazone (1288)+TX, mevinphos(556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX, milbemycin oxime(alternative name) [CCN]+TX, mipafox (1293)+TX, mirex (1294)+TX,monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternativename) [CCN]+TX, naftalofos (alternative name) [CCN]+TX, naled (567)+TX,naphthalene (IUPAC/Chemical Abstracts name) (1303)+TX, NC-170(development code) (1306)+TX, NC-184 (compound code)+TX, nicotine(578)+TX, nicotine sulfate (578)+TX, nifluridide (1309)+TX, nitenpyram(579)+TX, nithiazine (1311)+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1zinc chloride complex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250(compound code)+TX, nornicotine (traditional name) (1319)+TX, novaluron(585)+TX, noviflumuron (586)+TX, O-5-dichloro-4-iodophenyl O-ethylethylphosphonothioate (IUPAC name) (1057)+TX, O,O-diethylO-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate (IUPAC name)(1074)+TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-ylphosphorothioate (IUPAC name) (1075)+TX, O,O,O′,O′-tetrapropyldithiopyrophosphate (IUPAC name) (1424)+TX, oleic acid (IUPAC name)(593)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydemeton-methyl(609)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp′-DDT(219)+TX, para-dichlorobenzene [CCN]+TX, parathion (615)+TX,parathion-methyl (616)+TX, penfluoron (alternative name) [CCN]+TX,pentachlorophenol (623)+TX, pentachlorophenyl laurate (IUPAC name)(623)+TX, permethrin (626)+TX, petroleum oils (alternative name)(628)+TX, PH 60-38 (development code) (1328)+TX, phenkapton (1330)+TX,phenothrin (630)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone(637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosnichlor (1339)+TX,phosphamidon (639)+TX, phosphine (IUPAC name) (640)+TX, phoxim (642)+TX,phoxim-methyl (1340)+TX, pirimetaphos (1344)+TX, pirimicarb (651)+TX,pirimiphos-ethyl (1345)+TX, pirimiphos-methyl (652)+TX,polychlorodicyclopentadiene isomers (IUPAC name) (1346)+TX,polychloroterpenes (traditional name) (1347)+TX, potassium arsenite[CCN]+TX, potassium thiocyanate [CCN]+TX, prallethrin (655)+TX,precocene I (alternative name) [CCN]+TX, precocene II (alternative name)[CCN]+TX, precocene III (alternative name) [CCN]+TX, primidophos(1349)+TX, profenofos (662)+TX, profluthrin [CCN]+TX, promacyl(1354)+TX, promecarb (1355)+TX, propaphos (1356)+TX, propetamphos(673)+TX, propoxur (678)+TX, prothidathion (1360)+TX, prothiofos(686)+TX, prothoate (1362)+TX, protrifenbute [CCN]+TX, pymetrozine(688)+TX, pyraclofos (689)+TX, pyrazophos (693)+TX, pyresmethrin(1367)+TX, pyrethrin I (696)+TX, pyrethrin II (696)+TX, pyrethrins(696)+TX, pyridaben (699)+TX, pyridalyl (700)+TX, pyridaphenthion(701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, pyriproxyfen(708)+TX, quassia (alternative name) [CCN]+TX, quinalphos (711)+TX,quinalphosmethyl (1376)+TX, quinothion (1380)+TX, quintiofos (1381)+TX,R-1492 (development code) (1382)+TX, rafoxanide (alternative name)[CCN]+TX, resmethrin (719)+TX, rotenone (722)+TX, RU 15525 (developmentcode) (723)+TX, RU 25475 (development code) (1386)+TX, ryania(alternative name) (1387)+TX, ryanodine (traditional name) (1387)+TX,sabadilla (alternative name) (725)+TX, schradan (1389)+TX, sebufos(alternative name)+TX, selamectin (alternative name) [CCN]+TX, SI-0009(compound code)+TX, SI-0205 (compound code)+TX, SI-0404 (compoundcode)+TX, SI-0405 (compound code)+TX, silafluofen (728)+TX, SN 72129(development code) (1397)+TX, sodium arsenite [CCN]+TX, sodium cyanide(444)+TX, sodium fluoride (IUPAC/Chemical Abstracts name) (1399)+TX,sodium hexafluorosilicate (1400)+TX, sodium pentachlorophenoxide(623)+TX, sodium selenate (IUPAC name) (1401)+TX, sodium thiocyanate[CCN]+TX, sophamide (1402)+TX, spinosad (737)+TX, spiromesifen (739)+TX,spirotetrmat (CCN)+TX, sulcofuron (746)+TX, sulcofuronsodium (746)+TX,sulfluramid (750)+TX, sulfotep (753)+TX, sulfuryl fluoride (756)+TX,sulprofos (1408)+TX, tar oils (alternative name) (758)+TX,tau-fluvalinate (398)+TX, tazimcarb (1412)+TX, TDE (1414)+TX,tebufenozide (762)+TX, tebufenpyrad (763)+TX, tebupirimfos (764)+TX,teflubenzuron (768)+TX, tefluthrin (769)+TX, temephos (770)+TX, TEPP(1417)+TX, terallethrin (1418)+TX, terbam (alternative name)+TX,terbufos (773)+TX, tetrachloroethane [CCN]+TX, tetrachlorvinphos(777)+TX, tetramethrin (787)+TX, theta-cypermethrin (204)+TX,thiacloprid (791)+TX, thiafenox (alternative name)+TX, thiamethoxam(792)+TX, thicrofos (1428)+TX, thiocarboxime (1431)+TX, thiocyclam(798)+TX, thiocyclam hydrogen oxalate (798)+TX, thiodicarb (799)+TX,thiofanox (800)+TX, thiometon (801)+TX, thionazin (1434)+TX, thiosultap(803)+TX, thiosultap-sodium (803)+TX, thuringiensin (alternative name)[CCN]+TX, tolfenpyrad (809)+TX, tralomethrin (812)+TX, transfluthrin(813)+TX, transpermethrin (1440)+TX, triamiphos (1441)+TX, triazamate(818)+TX, triazophos (820)+TX, triazuron (alternative name)+TX,trichlorfon (824)+TX, trichlormetaphos-3 (alternative name) [CCN]+TX,trichloronat (1452)+TX, trifenofos (1455)+TX, triflumuron (835)+TX,trimethacarb (840)+TX, triprene (1459)+TX, vamidothion (847)+TX,vaniliprole [CCN]+TX, veratridine (alternative name) (725)+TX, veratrine(alternative name) (725)+TX, XMC (853)+TX, xylylcarb (854)+TX, YI-5302(compound code)+TX, zeta-cypermethrin (205)+TX, zetamethrin (alternativename)+TX, zinc phosphide (640)+TX, zolaprofos (1469) and ZXI 8901(development code) (858)+TX,

a molluscicide selected from the group of substances consisting ofbis(tributyltin) oxide (IUPAC name) (913)+TX, bromoacetamide [CCN]+TX,calcium arsenate [CCN]+TX, cloethocarb (999)+TX, copper acetoarsenite[CCN]+TX, copper sulfate (172)+TX, fentin (347)+TX, ferric phosphate(IUPAC name) (352)+TX, metaldehyde (518)+TX, methiocarb (530)+TX,niclosamide (576)+TX, niclosamide-olamine (576)+TX, pentachlorophenol(623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX,thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX,trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) andtriphenyltin hydroxide (IUPAC name) (347)+TX,

a nematicide selected from the group of substances consisting ofAKD-3088 (compound code)+TX, 1,2-dibromo-3-chloropropane (IUPAC/ChemicalAbstracts name) (1045)+TX, 1,2-dichloropropane (IUPAC/Chemical Abstractsname) (1062)+TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPACname) (1063)+TX, 1,3-dichloropropene (233)+TX,3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstractsname) (1065)+TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name)(980)+TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid (IUPACname) (1286)+TX, 6-isopentenylaminopurine (alternative name) (210)+TX,abamectin (1)+TX, acetoprole [CCN]+TX, alanycarb (15)+TX, aldicarb(16)+TX, aldoxycarb (863)+TX, AZ 60541 (compound code)+TX, benclothiaz[CCN]+TX, benomyl (62)+TX, butylpyridaben (alternative name)+TX,cadusafos (109)+TX, carbofuran (118)+TX, carbon disulfide (945)+TX,carbosulfan (119)+TX, chloropicrin (141)+TX, chlorpyrifos (145)+TX,cloethocarb (999)+TX, cytokinins (alternative name) (210)+TX, dazomet(216)+TX, DBCP (1045)+TX, DCIP (218)+TX, diamidafos (1044)+TX,dichlofenthion (1051)+TX, dicliphos (alternative name)+TX, dimethoate(262)+TX, doramectin (alternative name) [CCN]+TX, emamectin (291)+TX,emamectin benzoate (291)+TX, eprinomectin (alternative name) [CCN]+TX,ethoprophos (312)+TX, ethylene dibromide (316)+TX, fenamiphos (326)+TX,fenpyrad (alternative name)+TX, fensulfothion (1158)+TX, fosthiazate(408)+TX, fosthietan (1196)+TX, furfural (alternative name) [CCN]+TX,GY-81 (development code) (423)+TX, heterophos [CCN]+TX, iodomethane(IUPAC name) (542)+TX, isamidofos (1230)+TX, isazofos (1231)+TX,ivermectin (alternative name) [CCN]+TX, kinetin (alternative name)(210)+TX, mecarphon (1258)+TX, metam (519)+TX, metam-potassium(alternative name) (519)+TX, metam-sodium (519)+TX, methyl bromide(537)+TX, methyl isothiocyanate (543)+TX, milbemycin oxime (alternativename) [CCN]+TX, moxidectin (alternative name) [CCN]+TX, Myrotheciumverrucaria composition (alternative name) (565)+TX, NC-184 (compoundcode)+TX, oxamyl (602)+TX, phorate (636)+TX, phosphamidon (639)+TX,phosphocarb [CCN]+TX, sebufos (alternative name)+TX, selamectin(alternative name) [CCN]+TX, spinosad (737)+TX, terbam (alternativename)+TX, terbufos (773)+TX, tetrachlorothiophene (IUPAC/ChemicalAbstracts name) (1422)+TX, thiafenox (alternative name)+TX, thionazin(1434)+TX, triazophos (820)+TX, triazuron (alternative name)+TX,xylenols [CCN]+TX, YI-5302 (compound code) and zeatin (alternative name)(210)+TX,

a nitrification inhibitor selected from the group of substancesconsisting of potassium ethylxanthate [CCN] and nitrapyrin (580)+TX,

a plant activator selected from the group of substances consisting ofacibenzolar (6)+TX, acibenzolar-S-methyl (6)+TX, probenazole (658) andReynoutria sachalinensis extract (alternative name) (720)+TX,

a rodenticide selected from the group of substances consisting of2-isovalerylindan-1,3-dione (IUPAC name) (1246)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,alpha-chlorohydrin [CCN]+TX, aluminium phosphide (640)+TX, antu(880)+TX, arsenous oxide (882)+TX, barium carbonate (891)+TX,bisthiosemi (912)+TX, brodifacoum (89)+TX, bromadiolone (91)+TX,bromethalin (92)+TX, calcium cyanide (444)+TX, chloralose (127)+TX,chlorophacinone (140)+TX, cholecalciferol (alternative name) (850)+TX,coumachlor (1004)+TX, coumafuryl (1005)+TX, coumatetralyl (175)+TX,crimidine (1009)+TX, difenacoum (246)+TX, difethialone (249)+TX,diphacinone (273)+TX, ergocalciferol (301)+TX, flocoumafen (357)+TX,fluoroacetamide (379)+TX, flupropadine (1183)+TX, flupropadinehydrochloride (1183)+TX, gamma-HCH (430)+TX, HCH (430)+TX, hydrogencyanide (444)+TX, iodomethane (IUPAC name) (542)+TX, lindane (430)+TX,magnesium phosphide (IUPAC name) (640)+TX, methyl bromide (537)+TX,norbormide (1318)+TX, phosacetim (1336)+TX, phosphine (IUPAC name)(640)+TX, phosphorus [CCN]+TX, pindone (1341)+TX, potassium arsenite[CCN]+TX, pyrinuron (1371)+TX, scilliroside (1390)+TX, sodium arsenite[CCN]+TX, sodium cyanide (444)+TX, sodium fluoroacetate (735)+TX,strychnine (745)+TX, thallium sulfate [CCN]+TX, warfarin (851) and zincphosphide (640)+TX,

a synergist selected from the group of substances consisting of2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934)+TX,5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903)+TX,farnesol with nerolidol (alternative name) (324)+TX, MB-599 (developmentcode) (498)+TX, MGK 264 (development code) (296)+TX, piperonyl butoxide(649)+TX, piprotal (1343)+TX, propyl isomer (1358)+TX, S421 (developmentcode) (724)+TX, sesamex (1393)+TX, sesasmolin (1394) and sulfoxide(1406)+TX,

an animal repellent selected from the group of substances consisting ofanthraquinone (32)+TX, chloralose (127)+TX, copper naphthenate [CCN]+TX,copper oxychloride (171)+TX, diazinon (227)+TX, dicyclopentadiene(chemical name) (1069)+TX, guazatine (422)+TX, guazatine acetates(422)+TX, methiocarb (530)+TX, pyridin-4-amine (IUPAC name) (23)+TX,thiram (804)+TX, trimethacarb (840)+TX, zinc naphthenate [CCN] and ziram(856)+TX,

a virucide selected from the group of substances consisting of imanin(alternative name) [CCN] and ribavirin (alternative name) [CCN]+TX,

a wound protectant selected from the group of substances consisting ofmercuric oxide (512)+TX, octhilinone (590) and thiophanate-methyl(802)+TX, an insecticide selected from the group consisting of thecompound of formula A-1

the formula A-2

the formula A-3

the formula A-4

the formula A-5

the formula A-6

the formula A-7

the formula A-8

the formula A-9

the formula A-10

the formula A-11

the formula A-12

the formula A-13

the formula A-14

the formula A-15

the formula A-16

the formula A-17

the formula A-18

the formula A-19

the formula A-20

the formula A-21

the formula A-22

the formula A-23

the formula A-24

the formula A-25

and the formula A-26

and biologically active compounds selected from the group consisting ofAzaconazole (60207-31-0]+TX, Bitertanol [70585-36-3]+TX, Bromuconazole[116255-48-2]+TX, Cyproconazole [94361-06-5]+TX, Difenoconazole[119446-68-3]+TX, Diniconazole [83657-24-3]+TX, Epoxiconazole[106325-08-0]+TX, Fenbuconazole [114369-43-6]+TX, Fluquinconazole[136426-54-5]+TX, Flusilazole [85509-19-9]+TX, Flutriafol[76674-21-0]+TX, Hexaconazole [79983-71-4]+TX, Imazalil [35554-44-0]+TX,Imibenconazole [86598-92-7]+TX, Ipconazole [125225-28-7]+TX, Metconazole[125116-23-6]+TX, Myclobutanil [88671-89-0]+TX, Pefurazoate[101903-30-4]+TX, Penconazole [66246-88-6]+TX, Prothioconazole[178928-70-6]+TX, Pyrifenox [88283-41-4]+TX, Prochloraz [67747-09-5]+TX,Propiconazole [60207-90-1]+TX, Simeconazole [149508-90-7]+TX,Tebuconazole [107534-96-3]+TX, Tetraconazole [112281-77-3]+TX,Triadimefon [43121-43-3]+TX, Triadimenol [55219-65-3]+TX, Triflumizole[99387-89-0]+TX, Triticonazole [131983-72-7]+TX, Ancymidol[12771-68-5]+TX, Fenarimol [60168-88-9]+TX, Nuarimol [63284-71-9]+TX,Bupirimate [41483-43-6]+TX, Dimethirimol [5221-53-4]+TX, Ethirimol[23947-60-6]+TX, Dodemorph [1593-77-7]+TX, Fenpropidine [67306-00-7]+TX,Fenpropimorph [67564-91-4]+TX, Spiroxamine [118134-30-8]+TX, Tridemorph[81412-43-3]+TX, Cyprodinil [121552-61-2]+TX, Mepanipyrim[110235-47-7]+TX, Pyrimethanil [53112-28-0]+TX, Fenpiclonil[74738-17-3]+TX, Fludioxonil [131341-86-1]+TX, Benalaxyl[71626-11-4]+TX, Furalaxyl [57646-30-7]+TX, Metalaxyl [57837-19-1]+TX,R-Metalaxyl [70630-17-0]+TX, Ofurace [58810-48-3]+TX, Oxadixyl[77732-09-3]+TX, Benomyl [17804-35-2]+TX, Carbendazim [10605-21-7]+TX,Debacarb [62732-91-6]+TX, Fuberidazole [3878-19-1]+TX, Thiabendazole[148-79-8]+TX, Chlozolinate [84332-86-5]+TX, Dichlozoline[24201-58-9]+TX, Iprodione [36734-19-7]+TX, Myclozoline [54864-61-8]+TX,Procymidone [32809-16-8]+TX, Vinclozoline [50471-44-8]+TX, Boscalid[188425-85-6]+TX, Carboxin [5234-68-4]+TX, Fenfuram [24691-80-3]+TX,Flutolanil [66332-96-5]+TX, Mepronil [55814-41-0]+TX, Oxycarboxin[5259-88-1]+TX, Penthiopyrad [183675-82-3]+TX, Thifluzamide[130000-40-7]+TX, Guazatine [108173-90-6]+TX, Dodine [2439-10-3][112-65-2] (freie Base)+TX, Iminoctadine [13516-27-3]+TX, Azoxystrobin[131860-33-8]+TX, Dimoxystrobin [149961-52-4]+TX, enestroburin {Proc.BCPC, Int. Congr., Glasgow, 2003, 1, 93}+TX, Fluoxastrobin[361377-29-9]+TX, Kresoxim-methyl [143390-89-0]+TX, Metominostrobin[133408-50-1]+TX, Trifloxystrobin [141517-21-7]+TX, Orysastrobin[248593-16-0]+TX, Picoxystrobin [117428-22-5]+TX, Pyraclostrobin[175013-18-0]+TX, Ferbam [14484-64-1]+TX, Mancozeb [8018-01-7]+TX, Maneb[12427-38-2]+TX, Metiram [9006-42-2]+TX, Propineb [12071-83-9]+TX,Thiram [137-26-8]+TX, Zineb [12122-67-7]+TX, Ziram [137-30-4]+TX,Captafol [2425-06-1]+TX, Captari [133-06-2]+TX, Dichlofluanid[1085-98-9]+TX, Fluoroimide [41205-21-4]+TX, Folpet [133-07-3]+TX,Tolylfluanid [731-27-1]+TX, Bordeaux Mixture [8011-63-0]+TX,Copperhydroxid [20427-59-2]+TX, Copperoxychlorid [1332-40-7]+TX,Coppersulfat [7758-98-7]+TX, Copperoxid [1317-39-1]+TX, Mancopper[53988-93-5]+TX, Oxine-copper [10380-28-6]+TX, Dinocap [131-72-6]+TX,Nitrothal-isopropyl [10552-74-6]+TX, Edifenphos [17109-49-8]+TX,Iprobenphos [26087-47-8]+TX, Isoprothiolane [50512-35-1]+TX, Phosdiphen[36519-00-3]+TX, Pyrazophos [13457-18-6]+TX, Tolclofos-methyl[57018-04-9]+TX, Acibenzolar-S-methyl [135158-54-2]+TX, Anilazine[101-05-3]+TX, Benthiavalicarb [413615-35-7]+TX, Blasticidin-S[2079-00-7]+TX, Chinomethionat [2439-01-2]+TX, Chloroneb [2675-77-6]+TX,Chlorothalonil [1897-45-6]+TX, Cyflufenamid [180409-60-3]+TX, Cymoxanil[57966-95-7]+TX, Dichlone [117-80-6]+TX, Diclocymet [139920-32-4]+TX,Diclomezine [62865-36-5]+TX, Dicloran [99-30-9]+TX, Diethofencarb[87130-20-9]+TX, Dimethomorph [110488-70-5]+TX, SYP-LI90 (Flumorph)[211867-47-9]+TX, Dithianon [3347-22-6]+TX, Ethaboxam [162650-77-3]+TX,Etridiazole [2593-15-9]+TX, Famoxadone [131807-57-3]+TX, Fenamidone[161326-34-7]+TX, Fenoxanil [115852-48-7]+TX, Fentin [668-34-8]+TX,Ferimzone [89269-64-7]+TX, Fluazinam [79622-59-6]+TX, Fluopicolide[239110-15-7]+TX, Flusulfamide [106917-52-6]+TX, Fenhexamid[126833-17-8]+TX, Fosetylaluminium [39148-24-8]+TX, Hymexazol[10004-44-1]+TX, Iprovalicarb [140923-17-7]+TX, IKF-916 (Cyazofamid)[120116-88-3]+TX, Kasugamycin [6980-18-3]+TX, Methasulfocarb[66952-49-6]+TX, Metrafenone [220899-03-6]+TX, Pencycuron[66063-05-6]+TX, Phthalide [27355-22-2]+TX, Polyoxins [11113-80-7]+TX,Probenazole [27605-76-1]+TX, Propamocarb [25606-41-1]+TX, Proquinazid[189278-12-4]+TX, Pyroquilon [57369-32-1]+TX, Quinoxyfen[124495-18-7]+TX, Quintozene [82-68-8]+TX, Schwefel [7704-34-9]+TX,Tiadinil [223580-51-6]+TX, Triazoxide [72459-58-6]+TX, Tricyclazole[41814-78-2]+TX, Triforine [26644-46-2]+TX, Validamycin [37248-47-8]+TX,Zoxamide (RH7281) [156052-68-5]+TX, Mandipropamid [374726-62-2]+TX, thecompound of formula F-1

wherein Ra₅ is trifluoromethyl or difluoromethyl (WO2004/058723)+TX, thecompound of formula F-2

wherein Ra₆ is trifluoromethyl or difluoromethyl (WO2004/058723)+TX, theracemic compound of formula F-3 (syn)

wherein Ra₇ is trifluoromethyl or difluoromethyl (WO2004/035589)+TX, theracemic mixture of formula F-4 (anti)

wherein Ra, is trifluoromethyl or difluoromethyl (WO2004/035589)+TX, thecompound of formula F-5

which is an epimeric mixture of racemic compounds of formulae F-3 (syn)and F-4 (anti), wherein the ratio from racemic compounds of formula F-3(syn) to racemic cmpounds of formula F-4 (anti) is from 1000:1 to 1:1000and wherein Ra, is trifluoromethyl or difluoromethyl (WO2004/035589)+TX,the compound of formula F-6

wherein Ra₈ is trifluoromethyl or difluoromethyl (WO2004/035589)+TX, theracemic compound of formula F-7 (trans)

wherein Ra₉ is trifluoromethyl or difluoromethyl (WO03/074491)+TX, theracemic compound of formula F-8 (cis)

wherein Ra₉ is trifluoromethyl or difluoromethyl (WO03/074491)+TX, thecompound of formula F-9

which is a mixture of the racemic compounds of formulae F-7 (trans) andF-8 (cis), wherein the ratio of the racemic compound of formula F-7(trans) to the racemic compound of formula F-8 (cis) is 2:1 to 100:1;and wherein Ra₉ is trifluoromethyl or difluoromethyl (WO03/074491)+TX,

the compound of formula F-10

wherein R₁₀ is trifluoromethyl or difluoromethyl (WO2004/058723)+TX, theracemic compound of formula F-11 (trans)

wherein R₁₁ is trifluoromethyl or difluoromethyl (WO03/074491)+TX, theracemic compound of formula F-12 (cis)

wherein R₁₁ is trifluoromethyl or difluoromethyl (WO03/074491)+TX, thecompound of formula F-13

which is a racemic mixture of formulae F-11 (trans) and F-12 (cis), andwherein R₁₁ is trifluoromethyl or difluoromethyl (WO 03/074491)+TX, thecompound of formula F-14

(WO2004/058723)+TX, and the compound of formula F-15

[214706-53-3]+TX.

The references in brackets behind the active ingredients, e.g.[3878-19-1] refer to the Chemical Abstracts Registry number. Thecompouds of the formulae A-1 to A-26 are described in WO 03/015518 or inWO 04/067528. The above described mixing partners are known. Where theactive ingredients are included in “The Pesticide Manual” [The PesticideManual—A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin;The British Crop Protection Council], they are described therein underthe entry number given in round brackets hereinabove for the particularcompound; for example, the compound “abamectin” is described under entrynumber (1). Where “[CCN]” is added hereinabove to the particularcompound, the compound in question is included in the “Compendium ofPesticide Common Names”, which is accessible on the internet [A. Wood;Compendium of Pesticide Common Names, Copyright©1995-2004]; for example,the compound “acetoprole” is described under the internet addresshttp://www.alanwood.net/pesticides/acetoprole.htmL.

Most of the active ingredients described above are referred tohereinabove by a so-called “common name”, the relevant “ISO common name”or another “common name” being used in individual cases. If thedesignation is not a “common name”, the nature of the designation usedinstead is given in round brackets for the particular compound; in thatcase, the IUPAC name, the IUPAC/Chemical Abstracts name, a “chemicalname”, a “traditional name”, a “compound name” or a “development code”is used or, if neither one of those designations nor a “common name” isused, an “alternative name” is employed. “CAS Reg. No” means theChemical Abstracts Registry Number.

The active ingredient mixture of the compounds of formula I selectedfrom tables T1 to T99 with active ingredients described above comprisesa compound selected from tables T1 to T99 and an active ingredient asdescribed above preferably in a mixing ratio of from 100:1 to 1:6000,especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to1:20, even more especially from 10:1 to 1:10, very especially from 5:1and 1:5, special preference being given to a ratio of from 2:1 to 1:2,and a ratio of from 4:1 to 2:1 being likewise preferred, above all in aratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750.Those mixing ratios are understood to include, on the one hand, ratiosby weight and also, on other hand, molar ratios.

The mixtures comprising a compound of formula I selected from tables T1to T99 and one or more active ingredients as described above can beapplied, for example, in a single “ready-mix” form, in a combined spraymixture composed from separate formulations of the single activeingredient components, such as a “tank-mix”, and in a combined use ofthe single active ingredients when applied in a sequential manner, i.e.one after the other with a reasonably short period, such as a few hoursor days. The order of applying the compounds of formula I selected fromtables T1 to T99 and the active ingredients as described above is notessential for working the present invention.

The compositions can also comprise further solid or liquid auxiliaries,such as stabilizers, for example unepoxidized or epoxidized vegetableoils (for example epoxidized coconut oil, rapeseed oil or soya oil),antifoams, for example silicone oil, preservatives, viscosityregulators, binders and/or tackifiers, fertilizers or other activeingredients for achieving specific effects, for example bactericides,fungicides, nematocides, plant activators, molluscicides or herbicides.

The compositions according to the invention are prepared in a mannerknown per se, in the absence of auxiliaries for example by grinding,screening and/or compressing a solid active ingredient and in thepresence of at least one auxiliary for example by intimately mixingand/or grinding the active ingredient with the auxiliary (auxiliaries).These processes for the preparation of the compositions and the use ofthe compounds I for the preparation of these compositions are also asubject of the invention.

The application methods for the compositions, that is the methods ofcontrolling pests of the abovementioned type, such as spraying,atomizing, dusting, brushing on, dressing, scattering or pouring—whichare to be selected to suit the intended aims of the prevailingcircumstances—and the use of the compositions for controlling pests ofthe abovementioned type are other subjects of the invention. Typicalrates of concentration are between 0.1 and 1000 ppm, preferably between0.1 and 500 ppm, of active ingredient. The rate of application perhectare is generally 1 to 2000 g of active ingredient per hectare, inparticular 10 to 1000 g/ha, preferably 10 to 600 g/ha.

A preferred method of application in the field of crop protection isapplication to the foliage of the plants (foliar application), it beingpossible to select frequency and rate of application to match the dangerof infestation with the pest in question. Alternatively, the activeingredient can reach the plants via the root system (systemic action),by drenching the locus of the plants with a liquid composition or byincorporating the active ingredient in solid form into the locus of theplants, for example into the soil, for example in the form of granules(soil application). In the case of paddy rice crops, such granules canbe metered into the flooded paddy-field.

The compositions according to the invention are also suitable for theprotection of plant propagation material, for example seeds, such asfruit, tubers or kernels, or nursery plants, against pests of theabovementioned type. The propagation material can be treated with thecompositions prior to planting, for example seed can be treated prior tosowing. Alternatively, the compositions can be applied to seed kernels(coating), either by soaking the kernels in a liquid composition or byapplying a layer of a solid composition. It is also possible to applythe compositions when the propagation material is planted to the site ofapplication, for example into the seed furrow during drilling. Thesetreatment methods for plant propagation material and the plantpropagation material thus treated are further subjects of the invention.

Biological Examples %=Percent by Weight, Unless Otherwise SpecifiedExample B1 Activity Against Spodoptera littoralis (Egyptian CottonLeafworm)

(Larvicide, Feeding/Residual Contact Activity, Preventive)

Cotton leaf discs are placed on agar in a 24-well microtiter plate andsprayed with test solutions. After drying, the leaf discs are infestedwith 5 L₁ larvae. The samples are checked for mortality, repellenteffect, feeding behaviour, and growth regulation 3 days after treatment.In this test, compounds listed in Table P above show good activity. Inparticular compounds P.1, P.2, P.3, P.4, P.5, P.6, P.7, P.9, P.10, P.11,P.12, P.13, P.15, P.16, P.17, P.18, P.19, P.20, P.21, P.22, P.23, P.24,P.25, P.26, P.27, P.28, P.29, P.30, P.31, P.32, P.33, P.34, P.35, P.36,P.37, P.38, P.39, P.40, P.41, P.42, P.43, P.44, P.45, P.46, P.47, P.48,P.49, P.50, P.51, P.52, P.53, P.54, P.55, P.56, P.57, P.58, P.59, P.60,P.61, P.63, P.64, P.67, P.68 and P.70 show an activity of over 80% at aconcentration of 400 ppm.

Example B2 Activity Against Heliothis virescens (Tobacco Budworm)

(Ovo-Larvicide, Feeding/Contact Activity, Curative)

Eggs (0-24 h old) are placed in 24-well microtiter plate on artificialdiet and treated with test solutions by pipetting. After an incubationperiod of 4 days, samples are checked for egg mortality, larvalmortality, and growth regulation.

In this test, compounds listed in Table P above show good activity. Inparticular compounds P.1, P.2, P.3, P.4, P.5, P.6, P.7, P.9, P.10, P.11,P.12, P.13, P.15, P.16, P.17, P.18, P.19, P.20, P.21, P.22, P.23, P.25,P.26, P.27, P.28, P.29, P.30, P.31, P.32, P.33, P.34, P.35, P.36, P.37,P.38, P.39, P.40, P.41, P.42, P.43, P.44, P.46, P.47, P.48, P.49, P.50,P.51, P.52, P.53, P.54, P.55, P.56, P.57, P.58, P.59, P.60, P.61, P.63,P.64, P.67, P.68, P69, P.70, P.71, P.72, P.74, P.77 and P.78 show anactivity of over 80% at a concentration of 400 ppm.

Example B3 Plutella xylostella (Diamond Back Moth)

(Larvicide, Feeding/Residual Contact Activity, Preventive)

24-well microtiter plate (MTP) with artificial diet is treated with testsolutions by pipetting. After drying, the MTP's are infested with larvae(L2)(10-15 per well). After an incubation period of 5 days, samples arechecked for larval mortality, antifeedant and growth regulation. In thistest, compounds listed in Table P above show good activity. Inparticular compounds P.1, P.2, P.3, P.4, P.5, P.6, P.7, P.9, P.10, P.11,P.12, P.13, P.15, P.16, P.17, P.18, P.19, P.20, P.21, P.22, P.23, P.25,P.26, P.27, P.28, P.29, P.30, P.31, P.32, P.33, P.34, P.35, P.36, P.37,P.38, P.39, P.40, P.41, P.42, P.43, P.44, P.46, P.47, P.48, P.49, P.50,P.51, P.52, P.53, P.54, P.55, P.56, P.57, P.58, P.59, P.60, P.61, P.63,P.64, P.67, P.68, P.69 P.70, P.72, P.74, P.77, P78 and P.79 show anactivity of over 80% at a concentration of 400 ppm.

Example B4 Diabrotica balteata (Corn Root Worm)

(Larvicide, Feeding/Residual Contact Activity, Preventive)

24-well microtiter plate (MTP) with artificial diet is treated with testsolutions by pipetting. After drying, the MTP's are infested with larvae(L2)(6-10 per well). After an incubation period of 5 days, samples arechecked for larval mortality, antifeedant and growth regulation. In thistest, compounds listed in Table P above show good activity. Inparticular compounds P.1, P.2, P.5, P.6, P.10, P.11, P.12, P.13, P.15,P.16, P.17, P.18, P.19, P.24, P.25, P.27, P.28, P.29, P.30, P.31, P.33,P.34, P.35, P.37, P.38, P.39, P.42, P.43, P.44, P.45, P.46, P.47, P.48,P.49, P.50, P.52, P.53, P.65, P.67, P.68, P.69, P.70, P.71, P.72, P.75,P.78, and P.79 show an activity of over 80% at a concentration of 400ppm.

Example B5 Activity Against Myzus persicae (Green Peach Aphid)

(Mixed Population, Feeding/Residual Contact Activity, Preventive)

Sunflower leaf discs are placed on agar in a 24-well microtiter plateand sprayed with test solutions. After drying, the leaf discs areinfested with an aphid population of mixed ages. After an incubationperiod of 6 days, samples are checked for mortality and special effects(e.g. phytotoxicity).

In this test, compounds listed in Table P above show good activity. Inparticular compounds P.2, P.9, P.10, P.11, P.12, P.13, P.15, P.16, P.17,P.18, P.19, P.25, P.27, P.28, P.29, P.30, P.31, P.32, P.33, P.34, P.35,P.36, P.37, P.38, P.39, P.40, P.41, P.42, P.43, P.44, P.45, P.46, P.47,P.48, P.49, P.50, P.51, P.52, P.53, P.54, P.55, P.56, P.57, P.58, P.59,P.60, P.61 and P.70 show an activity of over 80% at a concentration of400 ppm.

Example B6 Activity Against Myzus persicae (Green Peach Aphid)

(Mixed Population, Systemic/Feeding Activity, Curative)

Roots of pea seedlings, infested with an aphid population of mixed ages,are placed directly in the test solutions. 6 days after introduction,samples are checked for mortality and special effects on the plant.

In this test, compounds listed in Table P above show good activity. Inparticular compounds P.10, P.12, P.13, P.15, P.17, P.19, P.27, P.28,P.29, P.30, P.32, P.33, P.34, P.35, P.36, P.37, P.39, P.40, P.42, P.43,P.44, P.45, P.46, P.47, P.48, P.49, P.50, P.51, P.52, P.53, P.54, P.55,P.56, P.57, P.58, P.59, P.60, P.61, P.65, P.70 and P.71 show an activityof over 80% at a concentration of 400 ppm.

Example B7 Activity Against Thrips tabaci (Onion Thrips)

(Mixed Population, Feeding/Residual Contact Activity, Preventive)

Sunflower leaf discs are placed on agar in a 24-well microtiter plateand sprayed with test solutions. After drying, the leaf discs areinfested with a thrips population of mixed ages. After an incubationperiod of 6 days, samples are checked for mortality and special effects(e.g. phytotoxicity).

In this test, compounds listed in Table P above show good activity. Inparticular compounds P.3, P.10, P.12, P.13, P.16, P.18, P.25, P.26,P.27, P.28, P.29, P.32, P.33, P.34, P.35, P.37, P.39, P.40, P.41, P.42,P.43, P.44, P.45, P.46, P.47, P.48, P.49, P.50, P.51, P.52, P.53, P.54,P.55, P.56, P.57, P.58, P.59, P.63, P.64, P.65, P.67, P.68, P.70 andP.71 show an activity of over 80% at a concentration of 400 ppm.

Example B8 Activity Against Cydia pomonella (Codling Moth)

Standard Cydia diet cubes (1.5 cm width) are pierced with a tooth-pickand are immersed in liquid paraffin (ca. 80° C.). After the paraffincoat has hardened, an aqueous emulsion containing 400 ppm of activeingredient is applied using a De Vilbis sprayer (25 ml, 1 bar). Afterthe spray coating has dried, the cubes are put into plastic containerswhich are then populated with two freshly hatched Cydia pomonella(1^(st) instar). The containers are then closed with a plastic cap.After 14 days incubation at 26° C. and 40-60% relative humidity, thesurvival rate of the caterpillars as well as their growth regulation isdetermined. In this test, compounds listed in Table P above show goodactivity. In particular compounds P.10, P.11, P.12, P.18, P.19, P.20,P.29, P.30, P.31, P.32, P.33, P.34, P.35, P.37, P.38, P.39, P.42, andP.43 show an activity of over 80% at a concentration of 400 ppm.

Example B9 Activity Against Frankliniella occidentalis (Western FlowerThrips)

Bean leaf discs on agar in petri dishes or bean plants in a spraychamber are treated with diluted test solutions. After drying leaf discsare cut and placed in plastic cups on the surface of an agar layer andinfested with mixed population. 6 days (leaf discs) or 14 days (plants)after the infestation, samples are checked for reduction of treatedpopulation and compared to the non treated population.

In this test, compounds listed in Table P above show good activity. Inparticular compounds P.10, P.11, P.12, P.13, P.15, P.17, P.18, P.19,P.22, P.27, P.28, P.30, P.33, P.34, P.35, P.38, P.39, P.40, P.41, P.42,P.43, P.44, P.45, P.46, P.47, P.48, P.49, P.52, P.54, P.56, P.60, P.61and P.70 show an activity of over 80% at a concentration of 400 ppm.

Example B9 Activity Against Bemisia tabaci (Tobacco White Fly)

(Larvicide, Contact/Feeding)

Bean plants are infested with 20-30 adults that removed after a 4 dayegg-laying period. After another 7 days, bean plants with hatched nymphs(N-2) are treated (2 replicates) with the test solutions in a spraychamber. Three weeks later, samples are checked for number of emergedadults. Efficacy was calculeted by comparing number of emerged adults intreated and non treated samples.

In this test, compounds listed in Table P above show good activity. Inparticular compounds P.10, P.12, P.18, P.19, P.29, P.30 and P.33 show anactivity of over 80% at a concentration of 400 ppm.

Example B9 Activity Against Nilaparvata lugens (Brown Rice Planthopper)

(Larvicide, Feeding/Contact)

Rice seedlings are treated with the diluted test solutions in a spraychamber. After drying, they are infested with 20 N₃ nymphs (2replicates). 6-12 days after the treatment samples are checked formortality, growth regulation, and effects on the F₁ generation.

In this test, compounds listed in Table P above show good activity. Inparticular compounds P.27, P.28, P.40, P.42, P.43, P.45 and P.47 show anactivity of over 80% at a concentration of 400 ppm.

Example B10 Activity Against Aphis craccivora (Pea Aphid)

(Mixed Population, Contact/Feeding)

Pea seedlings, infested with an aphid population of mixed ages, aretreated (2 replicates) with diluted test solutions in a spray chamber. 6days after treatment, samples are checked for mortality.

In this test, compounds listed in Table P above show good activity. Inparticular compounds P.10, P.27, P.28, P.30, P.40, P.42, P.43, P.44,P.46, P.47 and P.49, show an activity of over 80% at a concentration of400 ppm.

Example B11 Activity Against Aphis craccivora (Pea Aphid)

(Mixed Population, Systemic/Feeding)

Roots of pea seedlings, infested with an aphid population of mixed ages,are placed (2 replicates) directly in the test solution. 6 days later,samples are checked for mortality.

In this test, compounds listed in Table P above show good activity. Inparticular compounds P.10, P.13, P.27, P.28, P.30, P.33, P.39, P.40,P.42, P.43, P.44, P.45, P.46, P.47, P.49, P.52, P.54, P.56, P.60 andP.61 show an activity of over 80% at a concentration of 400 ppm.

Example B12 Activity Against Aphis qossvpii (Cotton Aphid)

(Mixed Population, Contact/Feeding)

Pea seedlings, infested with an aphid population of mixed ages, aretreated (2 replicates) with diluted test solutions in a spray chamber. 6days after treatment, samples are checked for mortality.

In this test, compounds listed in Table P above show good activity. Inparticular compounds P.10, P.27, P.40, P.42 and P.47 show an activity ofover 80% at a concentration of 400 ppm.

Example B13 Activity Against Aphis aossypii (Cotton Aphid)

(Mixed Population, Systemic/Feeding)

Roots of pea seedlings, infested with an aphid population of mixed ages,are placed (2 replicates) directly in the test solution. 6 days later,samples are checked for mortality.

In this test, compounds listed in Table P above show good activity. Inparticular compounds P.27, P.28, P.30, P.39, P.40, P.42, P.43, P.44,P.47, P.56, P.60 and P.61 show an activity of over 80% at aconcentration of 400 ppm.

Example B14 to B15 Comparison of the Insecticidal Activity of CompoundsAccording to the Invention with the Structurally Most Closely ComparableCompound from the State of the Art (Compound No. T81.3 Described on Page67 of WO2005/085234)

Example B14 Plutella xylostella (Diamond Back Moth)

(Larvicide, Feeding/Residual Contact Activity, Preventive)

24-well microtiter plate (MTP) with artificial diet is treated with testsolutions by pipetting. After drying, the MTP's are infested with larvae(L2)(10-15 per well). After an incubation period of 5 days, samples arechecked for larval mortality, antifeedant and growth regulation.

Results are shown in Table B14:

TABLE B14 Activity against Plutella xylostella (diamond back moth):Concentration Death rate (%) Compound: (ppm) after 5 days Comp. T81.3(state of the art) 50 100 Comp. T81.3 (state of the art) 12.5 60 Comp.T81.3 (state of the art) 3.1 0 Comp. T81.3 (state of the art) 0.8 0Comp. P.78 (invention) 50 100 Comp. P.78 (invention) 12.5 100 Comp. P.78(invention) 3.1 100 Comp. P.78 (invention) 0.8 50

Table B14 shows that compound No. P.78 according to the invention exertsa substantially better insecticidal action on Plutella xylostella thanthe compound from the state of the art. Especially at low applicationrates (12.5, 3.1 and 0.8 ppm) the compound according to the invention isfar superior to the compound of the state of the art. This enhancedeffect was not to be expected on the basis of the structural similarityof these compounds.

Example B15 Activity Against Heliothis virescens (Ovo-Larvicide Test)

Eggs (0-24 h old) are placed in 24-well microtiter plate on artificialdiet and treated with test solutions by pipetting. After an incubationperiod of 4 days, samples are checked for egg mortality, larvalmortality, and growth regulation.

Results are shown in Table B15:

TABLE B15 Activity Activity against Heliothis virescens (ovo-larvicidetest): Concentration Ovo-larvicidal activity Compound: (ppm) (%) after 4days Comp. T81.3 (state of the art) 50 80 Comp. T81.3 (state of the art)12.5 65 Comp. T81.3 (state of the art) 3.1 25 Comp. T81.3 (state of theart) 0.8 0 Comp. P.78 (invention) 50 80 Comp. P.78 (invention) 12.5 80Comp. P.78 (invention) 3.1 50 Comp. P.78 (invention) 0.8 50

Table B15 shows that compound No. P.78 according to the invention exertsa substantially better insecticidal action on Heliothis virescens thanthe compound from the state of the art. Especially at low applicationrates (12.5, 3.1 and 0.8 ppm) the compound according to the invention isfar superior to the compound of the state of the art. This enhancedeffect was not to be expected on the basis of the structural similarityof these compounds.

What is claimed is:
 1. A compound represented by formula T24:

wherein R_(1a) is hydrogen, C₁-C₄alkyl, C₂-C₄alkynyl, halogen or cyano;R₂₀ is hydrogen, C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl,C₁-C₆alkylsulfonyl-C₁-C₆alkyl, C₁-C₆alkylsulflnyl-C₁-C₆alkyl,thiethan-3-yl, thiethan-3-yl substituted by C₁-C₄alkyl,

R₁₀₀ is halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy orC₁-C₆haloalkoxy.
 2. A compound according to claim 1, wherein R_(1a) ischloro or methyl; R₂₀ is hydrogen, C₁-C₆alkyl,C₁-C₆alkylthio-C₁-C₆alkyl, C₁-C₆alkylsulfonyl-C₁-C₆alkyl,C₁-C₆alkylsulfinyl-C₁-C₆alkyl,

R₁₀₀ is trifluoromethyl, difluoromethyl, methoxy, bromo, chloro or2,2,2-trifluoroethoxy.
 3. A compound according to claim 2, whereinR_(1a) is methyl; R₂₀ is C₁-C₆alkyl; and R₁₀₀ is methoxy.
 4. Treatedplant propagation material wherein said plant propagation material istreated with a pesticidal composition that includes the compound ofclaim
 1. 5. Treated plant propagation material wherein said plantpropagation material is treated with a pesticidal composition thatincludes the compound of claim
 2. 6. Treated plant propagation materialwherein said plant propagation material is treated with a pesticidalcomposition that includes the compound of claim
 3. 7. A pesticidalcomposition comprising the compound of claim 1 and optionally one ormore auxiliaries.
 8. A pesticidal composition comprising the compound ofclaim 2 and optionally one or more auxiliaries.
 9. A pesticidalcomposition comprising the compound of claim 3 and optionally one ormore auxiliaries.
 10. A method for controlling insect or Acarina pests,which comprises applying a pesticidal composition to the pests or theirenvironment wherein the composition comprises the compound of claim 1.11. A method for controlling insect or Acarina pests, which comprisesapplying a pesticidal composition to the pests or their environmentwherein the composition comprises the compound of claim
 2. 12. A methodfor controlling insect or Acarina pests, which comprises applying apesticidal composition to the pests or their environment wherein thecomposition comprises the compound of claim
 3. 13. A method ofprotecting plant propagation material from the attack by insect orAcarina pests, which comprises treating said plant propagation materialor the area surrounding said propagation material with a pesticidalcomposition comprising the compound of claim
 1. 14. A method ofprotecting plant propagation material from the attack by insect orAcarina pests, which comprises treating said plant propagation materialor the area surrounding said propagation material with a pesticidalcomposition comprising the compound of claim
 2. 15. A method ofprotecting plant propagation material from the attack by insect orAcarina pests, which comprises treating said plant propagation materialor the area surrounding said propagation material with a pesticidalcomposition comprising the compound of claim 3.